Alkyl Halide 1631899631060

CONTENT
S.No Pages
1. Theory 04 – 34
2. EXERCISE - 1 35 – 40
3. EXERCISE - 2 [Level - 1] 41 – 44
4. EXERCISE - 2 [Level - 2] 45 – 47
5. EXERCISE - 3 48 – 56
6. EXERCISE - 4 [Level - 1] 57 – 66
7. EXERCISE - 4 [Level - 2] 67 – 71
8. ANSWER KEY 72 – 77
9. SOLUTION 78 – 112
Let's Crack it !
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Alkyl Halide
1.1 ALIPHATIC HALOGEN DERIVATIVES :

Compounds obtained by the replacement of one or more hydrogen atom(s) from hydrocarbons are known as
halogen derivatives. The halogen derivatives of alkanes, alkenes, alkynes and arenes are known as alkyl halide
(haloalkene), alkenyl halide (haloalkenes), alkynyl halides (haloalkynes) and aryl halides (halobenzenes) respectively.
Alkyl halides : Monohalogen derivatives of alkanes are known as alkyl halides
Structure of alkyl halides:
C X
Classification of alkyl halides :

(i) Primary halide : If the halogen bearing carbon is bonded to one carbon atom or with no carbon atom
Example :
CH3 – X, R – CH2 – X
(ii) Secondary halide : If two carbon atoms are bonded to the halogen bearing carbon.
Example :
X Cl
R – CH – R , CH3 – CH – CH 3
(ii) Tertiary halide : Three other carbon atom bonded to the halogen bearing carbon atom.
Example :
R CH3
R– C – X , CH3 – C – Cl
R CH3
Halolkanes can be classified into following three categories.

(i) Monohaloalkanes
(ii) Dihaloalkanes
(iii) Polyhaloalkanes
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Alkyl Halide
1.2 IUPAC NOMENCLATURE OF ALKYL HALIDES
S.N. Compound IUPAC name
CH3
1. CH3 – C – Cl 2 – Chloro-2-methylpropane
CH3
2. CH3 – CH – CH 2 – CH 2 3-Bromo-1-chlorobutane
Br Cl
3. CH 2 – CH – CH – CH 2 2-Bromo-1-chloro-4-fluoro-3-methylbutane
F CH 3 Br Cl
Cl
Br
4. 2-Bromo-1-chloro-3-iodocyclopentane
I
5. CH 3 – CH – CH 2 – CH2 – CH2 5-chloropentan-2-ol

OH Cl
6. F 5-Fluoropent-1-ene
CH3Cl
7. Chlorophenylmethane
CHCl2
8. Dichlorophenylmethane
CCl3
9. Trichlorophenylmethane
Cl Cl
10. 2,2-Bis(chloromethyl)-1,3-dichloropropane
Cl Cl
Br H
11. Cis-1,4-dibromocyclohexane
Br H
CH 3
CH–CH–CH3
12. 2-iodo-3-phenylbutane
I
Alkyl Halide
1.3 ISOMERISM IN HALOALKANES
S.N. Compound IUPAC name

1. Structural Isomerism
(a) Chain 1. CH3 – CH2 – CH2 – CH 2 – Cl 1-Chlorobutane
CH3 – CH – CH 2 – Cl 1-Chloro-2-methylpropane
CH3
2. CH3 – CH2 – CH 2 – CH 2 – CH2 – Cl 1-Chloropentane

CH 3
CH3 – CH – CH2 – CH 2 – Cl 1-Chloro-3-methylbutane
CH 3
CH 3 – CH – CH2 – Cl 1-Chloro-2,2-dimethylpropane
CH 3
(b) Position 1. CH3 – CH 2 – CH2 – Cl 1-Chloropropane

Cl
CH3 – CH – CH3 2-Chloropropane
2. CH3 – CH – CH2– Cl 1-Chloro-2-methylpropane

CH3
Cl
CH3 – CH – CH3 2-Chloro-2-methylpropane

CH3
2. Stereoisomerism
CH3 CH3
H * Cl Cl * H
` (a) Optical isomerism
CH2–CH3 CH2–CH3
(2S)-2-Cholobutane (2R)-2-Cholobutane
CH3 CH3
* CH3
H Cl Cl * H *
* H Cl Plane of
Cl H H * Cl
* symmetry
CH3 CH3 H Cl
CH3
Enantiomers of Meso-optically inactive
2,3-Dichlorobutane
Alkyl Halide
Mirror
Mirror
CH3 CH3
H Cl Cl H CH3 CH3
H Cl Cl H
Cl H H Cl
CH2CH3 CH2CH3 H Cl Cl H
CH 2CH 3 CH2CH3
Enantiomers
2,3-Dichloropentane Enantiomers
1.4 BONDING IN ALKYL HALIDE :
Table : 1 Carbon halogen bond lengths
Bond Bond length(Å)

CH3 – F 1.39
CH3 – Cl 1.78
CH3 – Br 1.93
CH3 – I 2.14
EXAMPLE
Classify the compound as a primary, secondary and tertiary halide
H3C CH3
Br
H
(a) (CH3)2CH–CH2Cl (b) Cl (c)
H H3C F
(d) CH 3 – CH – CH2Cl (e) Isopentyl bromide (f) Neopentyl iodide

CH3
Sol. (a) Primary (b) Secondary (c) Tertiary (d) Primary

(e) Primary (f) Primary
1.5 PHYSICAL PROPERTIES OF ALKYL HALIDE :
1.5.1 Dipole moment of the halogen derivatives:

 = 4.8 ×  × d
Where  is the charge and d is the bond length
These two effects e.g. charge and distance oppose each other, with the larger halogens having longer bond but
weaker electronegativity. The overall result is that the bond dipole moment increase in the order.
C – I < C – Br < C – F < C – Cl
: 1.29 D 1.48 D 1.51 D 1.56 D
The electronegativities of the halogen increase in the order:
I < Br < Cl < F
Alkyl Halide
Table : 2 Molecular dipole moments of methylhalides
X CH3X CH2X2 CHX3 CX4

F 1.82 D 1.97 D 1.65 D 0
Cl 1.94 D 1.60 D 1.03 D 0
Br 1.79 D 1.45 D 1.02 D 0
I 1.64 D 1.11 D 1.00 D 0
1.5.2 Boiling point :

(a) With respect to the halogen in a group of alkyl halides, the boiling point increases as one descends the periodic
table. Alkyl fluorides have the lowest boiling points and alkyl iodides have the highest boiling point. This trend
matches the order of increasing polarizability of the halogens. (Polarizability is the ease with which the electrons
distribution around an atom is distorted by a nearby electric field and is a significant factor in determining the
strength of induced-dipole/induced-dipole and dipole/induced-dipole attractions.) Forces that depend on induced
dipoles are strongest when the halogen is a highly polarizable iodine, and weakest when the halogen is a
nonpolarizable fluorine.
Table : 3 Boiling points of some alkyl halide in ºC (1 atm)
Formula X=F X = Cl X = Br X=I

CH 3– X – 78 – 24 3 42
CH 3– CH2X – 32 12 38 72
CH 3– CH2– CH2X –3 47 71 103
CH 3– (CH2)3– CH2X 65 108 129 157
CH 3– (CH2)4– CH2X 92 134 155 180
Fluorine is unique among the halogens is that increasing the number of fluorines does not lead to higher and higher
boiling point.
(b) The boiling points of the chlorinated derivatives of methane increase with the number of chlorine atoms
because of an increase in the induced-dipole/dipole attractive forces.
Compound CH3Cl CH2Cl2 CHCl3 CCl4
B.P. –24ºC 40ºC 61ºC 77ºC
Table : 4
CH3– CH2F CH3– CHF2 CH3– CF 3 CF3– CF3

B.P. -32ºC – 25ºC – 47ºC – 78ºC
1.5.3 Density :
Alkyl fluorides and chlorides are less dense and alkyl bromides and iodides more dense, than water.
Alkyl Halide
Table : 5
CH3– (CH2)6– CH2F CH3– (CH2)6– CH2Cl CH3– (CH2)6– CH2Br CH3– (CH2)6– CH2I
Density
0.80 g/mL 0.89 g/mL 1.12 g/mL 1.34 g/mL
(20ºC)
Because alkyl halides are insoluble in water, mixture of an alkyl halide and water separates into two layers. When
the alkyl halides in a fluoride or chloride, it is on the upper layer and water is the lower. The situation is reversed
when the alkyl halide is a bromide or an iodide. In these cases the alkyl halide is in the lower layer. Polyhalogenation
increases the density. The compounds CH2Cl2 CHCl3 and CCl4, for example, are all more dense than water.
1.6 PREPARATION OF ALKYL HALIDE :
1.6.1 From alkane :

X2/hv
R–H R – X + HX
1.6.2 From alkenes and alkynes (Detail in alkene and alkyne)
HX
C C –C–C–
(a)
H X
X2
C C –C–C–
(b)
X X
H X
2HX
(c) C C – C – C –
H X
X X
2X2
(d) C C –C–C–
X X
1.6.3 From alcohol (Detail in the alcohol)

HX, PX3,PX5, SOX2
R – OH R–X
1.6.4 From other halides

acetone
R – X + I– R – I + X–
R – Cl + KF 18-crown-6 R–F
Finkelstein Reaction
1. CH3 – CH2 – Cl NaI/acetone CH3 – CH2 – I
Nucleophility – in Polar Protic solvent
– F<Cl<Br<I
Polar Aprotic solvent
– F> Cl>Br> I
Covalent Nature : NaF < NaCl < NaBr < NaI
Alkyl Halide
Solubility in polar solvent 
CH3 – C – CH 3 CH3 – S – CH 3
O O
Acetone  Solubility in acetone is soluble
NaF < NaCl < NaBr < NaI
NaBr
2. C – C – Br Acetone
C – C – Br
NaCl
3. C – C – Cl Acetone
C – C – Cl
NaF
4. C – C – Cl Acetone
C–C–F
KF
5. C – C – Cl DMF
C – C – F (swart reaction)
or DMSO
Me Me
NaF
6. H Cl DMF F H
Et Et
Me
NaI
Acetone I H
Et
Me Me Me
NaI(excess)
7. H Cl Acetone I H +H I
(racemisation)
Et Et Et
1.7 CHEMICAL REACTIONS OF ALKYL HALIDE:
1.6.4 Nucleophilic substitution reaction:

Those organic compounds in which an sp3 hybridized carbon is bonded to an electronegative atom or group can
undergo two type of reaction e.g. substitution reactions in which the electronegative atom or group is replaced by
another atom or group. Second is elimination reaction in which the electronegative atom or group is eliminated
along with hydrogen from an adjacent carbon. The electronegative atom or group which is substituted or eliminated
is known as leaving group.
nucleophilic substitution
reaction
RCH2CH2 – Nu + X
RCH2CH2X + Nu
elimination reaction
the leaving group RCH = CH2 + NuH + X
Alkyl Halide
Because of more electronegativity of halogen atom it has partial negative charge and partial positive cha develops
on carbon atom.
RCH 2 – X
X = F, Cl, Br, I
Due to this polar carbon - halogen bond alkyl halides shows nucleophilic substitution and elimination reaction.
There are two important mechanisms for the substitution reaction
(1) A nucleophile is attracted to the partially positively charged carbon. As the nucleophile approaches the carbon,
it causes the carbon - halogen bond to break heterolytically (the halogen keeps both of the bonding electrons.)
Nu C C + X
X Nu
(2) The carbon-halogen bond breaks heterolytically without any assistance from the nucleophile, by the help of
polar protic solvent and carbocation is formed (solvolysis). Formed carbocation then reacts with the nucleophile
to form the substitution product.
+ Nu
C X C +X – C – Nu
(A) Bimolecular nucleophilic substitution reaction (SN2)

The mechanism of SN2 reaction
Nu + C–X Nu C X Nu – C + X
transition state
2
Characteristic of S N
(1) It is bimolecular, unistep process
(2) It is second order reaction because in the Rds two species are involved
(3) Kinetics of the reaction  rate  [alkyl halide] [nucleophile]

rate  k[alkyl halide] [nucleophile]
If the concentration of alkyl halide in the reaction mixture is doubled, the rate of the nucleophilic substitution
reaction is double. If the concentration of nucleophile is doubled the rate of reaction is also double. If the concentration
of both are doubled then the rate of the reaction quadriples.
(4) Energetics of the reaction 
Nu C X
transition state +
+
G The difference in free energy between
+ the reactant and the transition state.
Free energy
+
G
Gº The difference in free energy between
Nu + C –X the reactant and product.
Gº
Nu – C + X
Progress of reaction
Alkyl Halide
Figure : A free energy diagrams for a hypothetical SN2 reaction that takes place with a negative Gº
(5) No intermediates are formed in the SN2 reaction, the reaction proceeds through the formation of an unstable
arrangement of atoms or group called transition state.
(6) The stereochemistry of SN2 reaction  As we seen earlier, in an SN2 mechanism the nucleophile attacks from
the back side, that is from the side directly opposite to the leaving group. this mode of attack causes a inversion of
configuration at the carbon atom that is the target of nucleophilic attack. This inversion is also known as walden
inversion.
H H
walden
Nu Inversion
Nu – C H +
H H
H
(7) Factor's affecting the rate of SN2 reaction  Number of factors affect the relative rate of SN2 reaction, the
most important factors are
(i) Structure of the substrate
(ii) Concentration and reactivity of the nucleophile
(iii) Effect of the solvent
(iv) Nature of the leaving group
(i) Effect of the structure of the substrate 

Order of reactivity in SN2 reaction : – CH3 > 1º > 2º >> 3º (unreactive)
the important factor behind this order of reactivity is a steric effect. Very large and bulky groups can often hinder
the formation of the required transition state and crowding raises the energy of the transition state and slows
down reaction.
Table : 6 Relative rates of reactions of alkyl halide in SN2 reaction.
Substituent Compound Relative rate

Methyl CH3X 30
1º CH3CH2X 1
2º (CH3)2CHX 0.02
Neopentyl (CH3)3CCH2X 0.00001
3º (CH3)3CX ~0
(ii) According to kinetics of SN2 increasing the concentration of the nucleophile increases the rate of an SN2
reaction. The nature of nucleophile strongly affect the rate of SN2 reaction. A stronger nucleophile is much more
effective than a weaker. For example we know that a negatively charged nucleophile is more reactive than its
conjugate acid e.g. HO > H2O, RO > ROH.
Alkyl Halide
H H H
Inversion
R–O C–I R–O C I R–O–C + I
stronger
nucleophile
H H H H
H H
Lower Ea
H H
+ H
R – OH C–I R–O C I R–O–C + I
H H H H H H
H H
Higher Ea
Table : 7
some common nucleophiles listed in decreasing
order of nucleophilicity in hydroxylic solvent
Strong nucleophiles (CH 3CH2)3P Moderate nucleophile : Br
– SH NH3
I (CH3)2S
(CH3– CH2) 2NH Cl
– CN ACO
(CH3– CH 2)3N Weak nucleophile F
HO H2O
CH 3O CH3OH
Steric effects on nucleophilicity
CH3
CH3 C O
CH3 – CH2 – O
CH3

t-butoxide ethoxide weaker base,
Stronger base, yet weaker yet stronger nucleophile
nucleophile cannot approach
the carbon atom so easily.
(iii) The effect of the solvent In polar protic solvent large nucleophiles are good, and the halide ions show the
following order
I > Br > Cl > F (in polar protic solvent)
This effect is related to the strength of the interaction between nucleophile and solvent molecules of polar protic
solvent forms hydrogen bond to nucleophiles in the following manner.
Because small nucleophile is solvated more by the polar protic solvent thus its nucleophilicity decreases and rate
of SN2 decreases
Relative nucleophilicity in polar protic solvent
Alkyl Halide
SH > CN > I > OH > N3 > Br > ACO > Cl > F > H2O
So, polar protic solvents are not useful for rate of SN2, if nucleophile is anionic. But polar aprotic solvent does not
have any active hydrogen atom so they can not forms H bond with nucleophiles. Polar aprotic solvent have
crowded positive centre, so they do not solvate the anion appreciably therefore the rate of SN2 reactions increased
when they are carried out in polar aprotic solvent.
Examples of polar aprotic solvent.
CH3 CH3
H – C – N(CH3)2 CH3 – C – N(CH3)2
S
O O
O (DMA)
(DMF) (DMSO)
In DMSO, the relative order of reactivity of halide ions is

F > Cl > Br > I
(iv) The nature of the leaving group  The best leaving groups are those that become the most stable ion after
they leave, because leaving group generally leave as a negative ion, so those leaving group are good, which
stabilise negative charge most effectively and weak base do this best, so weaker bases are good leaving groups.
A good leaving group always stabilize the transition state and lowers its free energy of activation and thereby
increases the rate of the reaction.
Order of leaving ability of halide ion
I > Br > Cl > F
Other leaving groups are
O O
O S R O S O–R
O O
Alkanesulphonate ion Alkyl sulphate ion
O
O S CH3 CF3SO3
Triftlate ion
O
(a super leaving group)
Tosylate ion (OTs)
Strongly basic ions rarely act as leaving group 
Br + R – OH R – X + OH (strong base and bad lg)
Nu + CH3 – CH3 CH3 – Nu + CH3 (CH3 is strong base)
Table : 8 Examples of SN2 reactions of alkyl halide 
2
SN
Nu + CH3 – X Nu – R + X (X is not F)
Alkyl Halide
Nucleophile Product Class of Product
R – X +– I
R– I Alkyl halide
R – X +– OH
R – OH Alcohol
R – X +– OR'
R – OR' Ether
R – X + – SH
R – SH Thiol(mercaptan)
R – X +– SR'
R – SR' Thioether (sulphide)
–
R – NH3X Amine
R – X + NH3
+ +
R – X + – N = N = N– R – N = N = N– Azide
R– C C – R' Alkyne
R – X +– C C – R'
R– C N Nitrile
R – X +– C N
R – X + R' – COO – R – COO – R Ester
[R – PPh3]+ –
X Posphonium salt
R – X + P(Ph)3
EXAMPLE
Complete the following reactions with mechanism
OH
(i) Na
?
(a) CH2Cl
(ii)
CH2–Cl
OH ONa
Sol. (i) Na
+
O–CH2
Alkyl Halide
OH
KOH
(b) + CH3I 1 eq.
?
NO2
OCH3
Sol. (p-Nitroanisole)
NO2
OH
CH3CH2OH
(c) + Ph – CH2Cl
CH3CH2OK
excess
 
Sol. CH3–CH2–O is present in excess and it is stronger nucleophile than Ph – O so product is Ph–CH2 – OEt
Na CH3–CH2–I
(d) CH3 – C  CH X Y
Sol. CH 3 – C C + CH 3 – CH2 – I
CH 3 – C C – CH2 – CH3
CH2 Br
(e) + Ph3 P  Salt
CH2PPh3
Sol. Br
Ex. When the concentration of alkyl halide is tripled and the concentration of OH– ion is reduced
to half, the rate of SN2 reaction increases by :
(A) 3 times (B) 2 times (C) 1.5 times (D) 6 times
Ans. C
Ex. In the given reaction,

CH3CH2 – X + CH3SNa 
The fastest reaction occurs when 'X' is –
(A) – OH (B) – F (C) – OCOCF3 (D) OCOCH3
Ans. C
Alkyl Halide
Ex. Correct decreasing order of reactivity towards SN2 reaction
CH 3 CH3 CH3
(I) CH3CH2CHCH 2Cl (II) CH3CHCH2CH2Cl (III) CH3CH2CH2CH2Cl (IV) CH3CH2CH 2CH Cl
(A) IV > I > II > III (B) III > II > I > IV (C) IV > I > III > II (D) II > I > IV > III
Ans. B
Et
C2H5O
Q.1 CH3 – N CH2 Cl C2H5OH
?
CH 2
CH2Cl
Q.2 + KF 18-crown-6 Products.
What is the function of 8 corwn-6?
Q.3 Write mechanisms that account for the product of the following reactions:
CH2 CH2
OH
(a) HOCH2CH2Br H2O O
OH N
(b) NH2–CH2–CH2–CH2–CH2–Br H2O
H
Q.4 Draw a flscher projection for the product of the following SN2 reaction
CH3
H
Br H NaI (1 mole)/Acetone C
D
(a) H CH3 (b) + NH3
CH2CH3 Cl
(B) Unimolecular nucleophillic substitution reaction (SN1) :

Acetone
(CH3)3C – Cl + OH H2O
(CH3)3C – OH + Cl
Mechanism of S N
1
reaction :
Step - 1 Formation of a carbocation (Rate determining step)
R–X R + X
Step - 2 Nucleophillic attack on the carbocation (fast)
R + Nu R – Nu
Alkyl Halide
Characteristics of S N
1
reactions
1. It is unimolecular, two step process and intermediate is formed, (intermediate is carbocation)
2. It is first order reaction
3. Kinetics of the reaction

Rate  [Alkyl halide]
Rate = k[(CH3)3C–X]
Rate of SN1 reaction is independent of concentration and reactivity of nucleophile.
4. Energetics of the SN1
Intermediate
Ts(1) R – Nu
R–X
Ts(2)
+ R + Nu + X
Free energy
+ +
G1 +
G2
R – X + Nu
R – Nu + X
Figure : free energy diagram for the SN1 reaction.
5 Factor's affecting the rate of SN1

5.(i) The structure of the substrate 
The Rds of the SN1 reaction is ionization step, in this step carbocation is formed. This ionisation is strongly
endothermic process, rate of SN1 reaction depends strongly on carbocation stability because carbocation is the
intermediate of SN1 reaction which determines the energy of activation of the reaction.
SN1 reactivity : 3º > 2º > 1º > CH3 – X
5.(ii) Concentration and reactivity of the nucleophile 
The rate of SN1 reactions are unaffected by the concentration and nature of the nucleophile
5.(iii) Effect of the solvent the ioizing ability of the solvent:

Because to solvate cations and anions so effectively the use of polar protic solvent will greatly increase the rate
of ionization of an alkyl halide in any SN1 reaction. It does this because solvation stabilizes the transition state
leading to the intermediate carbocation and halide ion more than it does the reactant, thus the energy of activation
is lower.
Alkyl Halide
R–X R + X (Solvolysis)
O
H H
H H
O
H H
O R O H X H H
O
H H O
O H
H H H H
O
Solvated ions
Table : 9 Dielectric constants () and ionization rates of t-Butylchloride in common solvents
Solvent  Relative rate
H2O 80 8000
CH3OH 33 1000
C2H5OH 24 200
(CH3)2CO 21 1
CH3CO 2H 6 -
5.(iV) The nature of the leaving group 

In the SN1 reaction the leaving group begins to acquire a negative charge as the transition state is reached
stabilisation of this developing negative charge at the leaving group stabilizes the transition state and : this lowers
the free energy of activation and thereby increases the rate of reaction.
leaving ability of halogen is I > Br > Cl >> F

6. Stereochemistry of SN1 reactions In the SN1 mechanism, the carbocation intermediate is sp2 hybridized
and planar. A nucleophile can attack on the carbocation from either face,if reactant is chiral than after attack of
nucleophile from both faces gives both enantiomers of the product, which is called recemization.
Mechanism of recemization (SN1) 
Br R2 Nu Nu
Top attack
C C R1 C
R3 Solvlysis R3
R1 R3 R1
R2 R2
Nu Retention of
configuration
Bottom
Attack
R2
R3 R1
C
Nu
Inversion of
configuration
Alkyl Halide
Comparison of SN1 and SN2 reactions :
1 2
SN SN
Nucleophile strength
(i) Effect of the nucleophile is Stronger nucleophile is required
not important
(ii) Effect of the substrate 3o > 2o > 1o > CH3X CH3X > 1o >2o
It goes faster in less polar
Good ionizing solvent solvent,
(iii) Effect of solvent
required
if Nu is present
(iv) Kinetics Rate = k [R-X] Rate = k[R-X] [Nu ]
(v) Stereochemistry Racemisation walden inversion
(vi) Rearrangement common Impossible
EXAMPLE
Predict the compound in each pair that will undergo solvolysis (in aqueous ethanol) more rapidly.
I II
(a) (CH3CH2)2CH–Cl (CH3)3CCl
Br
(b)
Br
Br Br
(c)
Br Br
(d) O
Br Br
(e)
(CH3)2N–CH–CH3 NH2–CH–CH3
Sol. (a) II > I (b) II > I (c) I > II (d) II > I (e) II > I
EXAMPLE
Give the solvolysis products expected when each compound is heated in ethanol
Br
Br
Br
(a) (b) (c) Br
(d)
OC2H 5
OC2H5
Sol. (a) (b) (c) (d)
OC2H 5 OC2H5
Alkyl Halide
EXAMPLE
The rate of SN1 reaction is fastest with
(A) CH (B) CH
Br Br
(C) CH (D) ––CH2 – Br

Br
Ans. (A)
Reaction of RX with aq. KOH
Aq.KOH
1. R – Cl 2
R – OH + KCl
SN
Aq.KOH
2. CH3–CH2–Cl CH3–CH2–OH
Cl OH
Aq.KOH
3. CH3–CH CH3–CH –H2O CH3–CHO
Cl OH
Cl OH
Aq.KOH
4. CH3–C Cl CH3–C OH CH3COOH
Cl OH
Aq.KOH
5. C – C – C – C – Br C – C – C – C – OH
I OH
Aq.KOH
6.
14 14
7. C=C–C–I C = C – C – OH + C = C – C14 – OH
Me
Aq. KOH
HO H
CH3
Et
H Cl
Me Me
8.
Et (i)NaI/Acetone Aq. KOH
I H H OH
(ii) Aq. KOH
Et Et
Alkyl Halide
Other Nucleophilic reaction of R – X :–
RmgX
R–Me
RNa
R–Me (Wurtz Reaction)
R2Zn
R–Me (R2Zn is Frankland Reagent)
R2CuLi
R – Me (R2CuLi is Gilman's Reagent)
R–C CNa
R–C C – Me
NH3
H3N Me–Cl Me–NH2+HCl
MeNH2
Me–NH–Me
Me2NH
Me3N
Me3N
Me—Cl Me3N Me–Cl Me4N Cl
H2S/heat
MeSH + HCl
KCN (K C N)
Me–CN + Me – N C)
(major product) (minor product)
AgCN
Me–NC (methyl isocyanide)
KNO2
(CH3– O – N = O + CH3 – NO2)
(major product) (Minor product)
AgNO2
Me–NO2
(Ag–O–N=O)
RONa
ROMe (Williumson's ether synthesis)
RSNa
RSMe (Thioether)
Alkyl Halide
Williumson's Ether Synthesis: (SN2)
1. R O Na + R – Cl R – O – R + NaCl
2. EtONa + Me – Cl  EtOMe
3. MeONa + Et – Cl EtOMe
Rate (2) > (3) 2 is better method. (Due to less steric hindrence)
(lone pair is in resonance)

4. MeONa + PhCl No reaction
5. PhONa + MeCl PhOMe + NaCl
6. Me3CONa+ MeCl Me3COMe + NaCl
CH3
7. MeONa + Me3C – Cl Elimination CH 2 = C + MeOH + NaCl Major
CH3
8. PhONa + Me3C–Cl Elimination
CH3
CH 2 = C + PhOH + NaCl
CH3
9. Me3CONa + Ph–Cl No. reaction

Me3CO–Ph can not prepared by willionson's ether synthesis.
2
1. EtCl + NH3
SN
EtNH2 + HCl
2. NH3
C – C – C – Cl 2 C – C – C – NH2 + HCl
SN
Me Me
2
SN
3. D Br + NH3 H2N D + HCl
H H
H
Br N H
4. + N + HBr
H
5. + Me–I (Pyridinium salt)

N N I
Pynidine
Me
Alkyl Halide
Some Other reactions

Hydrolysis of Ether
18 H3O 18
1. MeOEt Et – OH + MeOH
18 18
H3O
2. MeOEt Et – OH + Me – OH
H3O
18 18
3. O O OH OH
18
H
+
O O H O O OH O
H
+
+
–H H
HOH O
HO HO
OH O
4.
-H3O+
HOH
HO O HO HO O HO HO HO O
H H
Me Et Me Et Me Et
H3O H3O
H O H H HO H H OH HO H
5.
D D D D D D
Reaction of ether with HI :
1. Me – O – Et 2
MeI + EtOH
SN
anhydrous HI
2. Me3CI + MeOH (Due to formation of more stable carbocation)
Conc.HI
Me3C–O–Me Me3CI + MeOH
conc.HI(excess)
Me3CI + MeOH
Alkyl Halide
With moist and dry Ag2O :
Alcoholic
(Major)
KOH
Cl
1. Moist Ag2O
OH(Major)
Ag2O
2. 2Me – Cl dry
Me – O – Me + 2AgCl
Ag2O
3. Me – Cl + EtCl dry
Me – O – Et + Me – O – Me + EtOEt
SNi (Nucleophilic substitution intramolecular )

(Darzon’s process)
Cl
..
R OH + S = O R Cl + SO2 (g) + HCl (g)
Cl
Mech.
Cl H
.. Cl
R OH + S = O R O O
S O
Cl
Cl
HCl(g)
O
R S=O
Cl
R – Cl + O = S = O (g)
Note : (1) In SNi retention of configuration takes place.
Note : (2) In presence of pyridene above reaction follow the SN2 reaction mechanism.
SNNGP(Neighbouring group participation)

Increase in rate of SN reaction due to attack of internal nucleophie is called as SNNGP is also known as Anchimeric
assistence.
For SNNGP:–
1. Internal nucleophile must be present
2. Internal nucleophile must be anti to lg.
Alkyl Halide
During NGP :–
Aq. KOH
H Cl 2 H H
SN
1.
Me H Me OH
Aq. KOH OH
H Cl H OH + OH H
SNNGP
2. (enantiomers)
OMe H O OMeH H OMe
Me
Aq. KOH
H Cl H OH
SNNGP
3. + (enantiomer)  Rate 3 > 2 > 1
MeS H MeS H
14 14
MeONa
MeS – CH2 – CH2 – Br CH2 – CH2
S
Me
4.
MeO 14 14
CH 2 – CH2 + CH 2 – CH2
SMe OMe OMe SMe
1.7.2 Elimination reactions:

In an elimination reaction two atoms or groups (YZ) are removed from the substrate with formation of pi bond.
Elimination
C C C C
-Y Z
Y Z
depending on the reagents and conditions involved, an elimination may be a first order (E1) or second order (E2).
Dehydration of Alohol (E1)
Conc.H2SO4
CH 3–CH 2 – OH CH 2=CH2
H –H
– H2O
CH 3–CH 2 – OH2 CH3–CH2
Characteristics of E1 reaction :
(i) It is unimolecular, two step process
(ii) It is first order reaction
(iii) Reaction intermediate is carbocation, so rearrangement is possible
Alkyl Halide
(iv) In the second step, a base abstracts a proton from the carbon atom adjacent to the carbocation, and forms
alkene.
(v) Kinetics  Rate  [Substrate]
Rate  k[Substrate]
Ts(1)
Ts(2)
H H
C C C C
H H
H
B
P.E.
H H
H C C H
H H
B
E2- elimination :
B H–CH2 – CH2 – lg CH2 = CH2 + lg
B H B H
H H H H
C C C C
H H
lg
H H
lg
T.S.
TS
H H
C C
P.E.
H H
reaction progress
Bimolecular reaction, second order kinetic.
1. Leaving group leads when base is taking proton from adjecent carbon.
2. It is a single step reaction
Alkyl Halide
3. Rate  single step reaction

Rate  Leaving group tendency
4. It shows elimental as well as kinetic isotopic effect with lg as well as at -position.
5. Normally saytzaff product is major.
6. Transition state machenism therefor rearrangement is not possible.

7. The orientation of proton & leaving group should be antiperiplanar for E2.
8. Positional orientation of elimination  In most E1 and E2 eliminations gives two or more possible elimination
products, the product with the most highly substituted double bond will predominate. This rule is called the saytzeff
or zaitsev rule (i.e., most stable alkene will be the major product)
9. E2–elimination is favour by :
(1) Moderate lg
(2) Strong base (RO, Alc. KOH)
(3) Polar aprotic solvent.
(4) High conc. of base.
(5) High temperature
Reactivity towards
E2  R – I > R – Br > R – Cl > R – F
EXAMPLE
Predict the elimination products of the following reactions.
(a) Sec. butyl bromide + NaOEt

(b) 3-Bromo-3-ethylpentane + CH3OH
(c) 2–Bromo-3-ethylpentane + MeONa
(d) 1-Bromo-2-methylcyclohexane + EtONa
CH2 CH 3
Sol. (a) CH3 – CH = CH –CH3 (b) CH3 – CH2 – C – CH2 – CH 3
OCH3
CH2 CH3 CH 3
(c) CH3 – CH 2 = C (d)
CH2 CH3
EXAMPLE
CH 3
Br CH3CH2ONa major + minor
CH3CH2OH
Write the structure of major and minor product.

CH2 CH 3
Sol. (minor) (major)
Alkyl Halide
Comparison of E1 and E2 elimination:
Promoting factors E1 E2
(i) Base Weak base Strong base required
(ii) Solvent Good ionizing solvent Wide variety of solvent
(iii) Substrate 3º > 2º > 1º 3º > 2º > 1º
(iv) Leaving group Better one required Better one required
Characteristics
st st
(i) Kinetics K[R– X], I order K[R – X] [Base], II order
(ii) Orientation Saytzeff alkene Saytzeff alkene
(iii) Stereochemistry No special geometry transition state
is required must be co-planar
EXAMPLE
CH 3
CH3OH,
CH3 P+Q+R
Cl
CH 3 CH 3
CH 3
CH 3 CH 3 CH3
Sol. P is , Q is ,R
OCH3 OCH3
Q.6 Arrange the compounds of each set in order of reactivity towards dehydrohalogenation by strong base
(a) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(b) 1-Bromo-3-methylbutane, 2-bromo-2-methylbutane-2-Bromo-3-methylbutane
(c) 1-Bromobutane,1-Bromo-2,2-dimethylpropane, 1-bromo-2-methylbutane, 1-Bromo-3-methylbutane
(C) mechanism of E1 CB reaction (Unimolecular conjugate base reaction) :

The E1 CB or carbanion mechanism : In the E1 CB, H leaves first and then the X. This is a two step process, the
intermediate is a carbanion.
Mechanism:
Step-1 : Consists of the removal of a proton, H by a base generating a carbanion
H
Base
C C X C C X
Step-2 : Carbanion loses a leaving group to form alkene
–X
C C X C C
Alkyl Halide
Condition: For the E1 CB, substrate must be containing acidic hydrogens and poor leaving groups (i.e., bad g)
B
H F F
Ex. X2C – C – F X2C – C – F X2C = CF2 + F
F F
1.8 Polyhalogen derivatives

Trichloromethane (Chloroform), CHCl3
1.8.1 Preparation
CH4 + Cl2 CH3Cl + HCl
Chloromethane
CH3Cl + Cl2 CH2Cl2 + HCl
Dichloromethane
CH2Cl2 + Cl2 CHCl3 + HCl
Trichloromethane
CHCl3 + Cl2 CCl4 + HCl
Tetrachloromethane
The mixture of CH3Cl, CH2Cl2, CHCl3 and CCl4 can be separated by fractional distillation.
2. From chloral hydrate, Pure chloroform can prepare.

NaOH + CCl3CHO  HCOONa + CHCl3
chloral
NaOH + CCl3CH(OH)2  HCOONa + CHCl3 + H2O
Chloral hydrate sodium formate Chloroform
3. Laboratory Method : From ethanol or acetone by reaction with a paste of bleaching powder and water.
In case of ethanol, the reaction occurs as follows

CaOCl2 + H2O  Ca(OH)2 + Cl2
Oxidation
CH3CH2OH + Cl2 CH3CHO + 2HCl
CH3CHO + 3Cl2 Chlorination CCl3CHO + 3HCl
Chloral
Ca(OH)2 + 2CCl3 CHO Hydrolysis 2CHCl3 + (HCOO)2Ca
Chloroform Calcium formate
4. From carbontetrachloride
Fe/H2O
CCl4 + 2[H] Heat
CHCl3 + HCl (partial reduction)
5. Haloform reaction
O O
–
R – C – CH3 + 3X2 + 3OH R – C – CX3 + 3X– + 3H2O
methyl ketone methyl ketone trihalomethyl
ketone
Alkyl Halide
–
O O
O O
– –
R – C – CX3 OH R – C – CX3 R–C CX3 R – C – + CHX3
O H O
OH
nucleophilic acyl a carboxylate a
substitution haloform ion
(Haloform)
Step 1 : Attack of the Step 2 : Elimination Step 3 : Proton transfer
nucleophile of the leaving group
Prob. Compare rate of elimination (Dehydro halogenation in presence of alcoholic KOH ) i.e., E2 :
Cl Cl Cl Cl
1. (a) (b) (c) (d)
c>b>a>d
2. (a) (b)
Br Br
c>b>a
Br
(c)
I
I
3. (a) (b)
c>b>a
I
(c)
I
I
4. (a) (b)
b>a>c
(c)
Alkyl Halide
Dehyodro halegenation (–HX) E2
Aq.KOH
CH 3 – CH2 – Cl CH3 – CH 2 – OH
Alc. KOH
CH2=CH 2
OH
H HO H
H H H H
C -----– C C -----– C
H H H H
Cl Cl
Anti elimination
Dehalogenation : – (–X2) E2
+2 –
Zn Zn +2e
CH 2 – CH2 CH2 = CH2 + ZnX2

X X
2e
X
H H
C -----– C
H H
X
Anti elimination
Ec or Ei (Intramolecular or cyclic elimination mechanism):
(1) Lg and Base present in same molecule
(2) It proceeds by cyclic transition state.
(3) Overall it is syn ellimination.
(4) Hoffmann is major product as it is obtain by least hinberd site/cyclic transition state.
(5) No rearrangement.
Alkyl Halide
Example of Ec/Ei
Pyrolysis of Ester :
O
R – C – O – CH2 – CH3 CH2=CH2 + RCOOH
base
O H O H
R–C CH2 R–C CH2
O CH2 O CH2
1. CH3–CH2–CH2–C–O–CD 2–CH3
Ec /Ei
CH 2=CD2 +CH3CH 2CH 2COOD
18
O
CH3–CH2–CH2–C–O–CH2–CH2–CH3
EC /Ei
O
18
2. CH3–CH=CH2+CH3CH2–C–OH
1.8.2 Physical properties of chloroform

Chloroform is a colourless, heavy liquid which has sweetish, sickly odour and taste. It boils at 334º K and is slightly
soluble in water. It is heavier than water. As inhaling of the vapours of chloroform induces unconsciousness
therefore it can be used as an anaesthetic agent for surgery.
1.8.3 Chemical properties of chloroform

1. Action of sun light and air
Sun light
2 CHCl3 + O2 2COCl2 + 2HCl
Phosgene
As chloroform is used for anaesthetic purposes, therefore in order to maintain a high purity of chloroform, this
reaction can be avoided by storing it in dark bottles, completely filled upto brim. The use of dark bottles (brown or
blue) cuts off active light radiations and filling upto brim keeps out air. Apart from this a small amount of enthanol
(1%) is usually added to bottles of chloroform. Addition of a little ethanol fixes the toxic COCl2 as non-poisonous
diethyl carbonate.
COCl2 + 2C2H5OH
O = C(OC2H5) + 2HCl
diethyl carbonate
Alkyl Halide
2. Hydrolysis :
–3KCl
H – CCl3 + (aq.) 3KOH –H2O
+KOH
H–C–O–H –H2O HCOOK
O
3. Reduction :
Zn + 2HCl ZnCl2 + 2[H]
CHCl3 + 2[H] CH2Cl2 + HCl
Dichloromethane
(Methylene chloride)
CHCl3 Zn + H2O CH4 + 3HCl
4. Reaction with acetone :
CH3
KOH
(CH3)2C = O + CHCl3 CH3 C OH
CCl3
Chlroetone
Use : Chloretone is used as hypnotic
(a sleep inducing) drug.
5. Reaction with nitric acid

2CHCl3 + HONO2 CCl3. NO2 + H2O
(chloropicrin)
Use : Chloropicrin is used as an insecticide and war gas.
6. Reaction with silver powder :

Heat
2CHCl3 + 6 Ag CH  CH + 6 AgCl
(Acetylene)
7. Chlorination :
hv
CHCl3 + Cl2 CCl4 + HCl
8. Reimer-Tiemann reaction:
OH
OH
CHO
333-343 K
+ CHCl3 + 3NaOH + 2NaCl + 2H2O
Salicylaldehyde
Phenol (2-Hydroxybenzeldehyde)
1.8.4 Uses of chloroform

1. As solvent in oils and varnishes
2. As preservative for anatomical specimens
3. As laboratory reagent
4. As an anaesthetic
Alkyl Halide
Exercise - 1 Objective Problems | JEE Main

Preparation Methods Of Alkyl halide
1. In reaction
C2H5OH + HX ZnX
2  C2H5X + H2O
the order of reactivity of HX is -
(A) HBr > HI > HCl (B) HI > HCl > HBr (C) HCl > HBr > HI (D) HI > HBr > HCl
2. Which of the following leads to the formation of an alkyl halide -

(A) C2H5OH Re
dP  Br2
 (B) C2H5OH SOCl
2 
(C) C2H5OH KBr

  Conc.H 2SO 4
  (D) All
3. Which reaction is termed as Darzen’s Reaction

(A) ROH + HCl (B) ROH + PCl5 (C) ROH + SOCl2 (D) ROH + PCl3
4. Silver benzoate reacts with bromine in acetone to form -
Br COBr COOAg
(A) (B) (C) (D)

Br
5. The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because -
(A) Alkyl chlorides are immiscible with SOCl2
(B) The other products of the reaction are gaseous and escape out
(C) Alcohol and SOCl2 are soluble in water
(D) The reaction occurs via intermediate formation of an alkyl chloro sulphite
6. The best reagent for converting ethanol to chloroethane is -

(A) PCl3 (B) PCl5 (C) SOCl2 (D) HCl + ZnCl2
7. In Hunsdiecker reaction -
(A) A sodium salt of an acid reacts with bromine
(B) A calcuim salt of an acid reacts with HBr
(C) A silver salt of an acid reacts with bromine
(D) A silver salt of an acid reacts with HBr
Chemical Reaction Of Alkyl Halide

8. Finkelstein reaction is -
(A) 2CH3CH2Cl+ Ag2O (dry)  CH3CH2OCH2CH3+ 2AgCl
(B) CH3CH2Br + NaI Acetone
  CH3CH2I+ NaBr
(C) CH3CH2Br + Ag2O (moist)  CH3CH2OH + AgBr
(D) CH3CH2Cl + NaOCH3  CH3 CH2OCH3 + NaCl
Alkyl Halide
9. The reaction of silver carboxylates with bromine dissolved in carbon tetrachloride is called
(A) Hofmann reaction (B) Borodine reaction
(C) Borodine - Hunsdiecker reaction (D) Hypobromide reaction
10. In Finkelstein Reaction, which reactants are used -

(A) NaI + C2H5OH (B) NaCl + acetone
(C) NaBr + CH3COCH3 (D) NaI + CH3COCH3
11. C2H5Cl + AgF C2H5F + AgCl

The above reaction is called -
(A) Hunsdiecker (B) Swart (C) Strecker (D) Wurtz
12. Which chloride is the most reactive towards aqueous NaOH in -

(A) Methyl chloride (B) Chlorobenzene (C) Vinyl chloride (D) Benzyl chloride
13. The S 2 reactivity order for halides :-

N
(A) R–F > R–Cl > R–Br > R–I (B) R–I > R–Br > R–Cl > R–F
(C) R–Br > R–l > R–Cl > R–F (D) R–Cl > R–Br > R–F > R–I
14. In SN1 reaction, the first step involves the formation of -

(A) Free radical (B) Carbanion (C) Carbocation (D) Final product
15. The rate law for the reaction, RCl + Na (a)  ROH + NaCl is given by, rate = K1 [RCl]. The rate of the reaction
will be -
(A) Doubled on doubling the concentration of sodium hydroxide
(B) Halved on reducing the concentration of alkyl halide to half
(C) Decreased on increasing the temperature of the reaction
(D) Unaffected by increasing the temperature of the reaction
16. Chlorobenzene is -
(A) More reactive than ethyl bromide (B) More reactive than isopropyl chloride
(C) As reactive as methyl chloride (D) Less reactive than benzyl chloride
17. Vinylic halides are unreactive towards nucleophilic substitution because of the following except -
(A) C - halogen bond is strong
(B) The halogen is bonded to sp2 carbon
(C) A double bond character is developed in the carbon-halogen bond by reasonance
(D) Halide ions are not good leaving groups
18. When an alkyl halide reacts with an alkoxide, the product is-
(A) Ether (B) Ester (C) Hydrocarbon (D) Alcohol
Alkyl Halide
CH3–CH–CH–CH3 SN1 / C2H5ONa

19. Ether
CH3 Br Williamson Re action
Ether is -
OC2H5
CH3–CH–CH–CH3
(A) CH3–C–CH2–CH3 (B) (C) Both correct (D) None is correct
CH3 OC2H5
CH3
20. (A) Cl


2 (B) aq
  (C) (
.KOH O)
 CH3CHO, Identify A, B & C -
(A) Ethylalcohol Ethyl chloride & Ethane

(B) Ethane, Ethylchloride & CH3–CH2–OH
(C) Propane, Propylchloride & CH3–CH2–CH2–OH
(D) All the above
21. An alkyl halide reacted with a metal cyanide to give an alkanenitrile. The metal cyanide is -
(A) AgCN (B) KCN (C) Cu2(CN)2 (D) Ba(CN)2
22. A strong solution of alcoholic alkali will preferentially promote alkyl halide into an alkene by
(A) Addition (B) Elimination (C) Polymerisation (D) Substitution
23. When ethyl bromide is treated with moist Ag2O the product is -
(A) Ethyl ether (B) Ethanol (C) Ethoxy ethane (D) All of the above
24 A carbon compound A forms B with sodium metal and again A forms C with PCl5 but B and C form diethylether.
Therefore A, B & C are -
(A) C2H5OH, C2H5 ONa, C2H5Cl (B) C2H5Cl, C2H5 ONa, C2H5 OH
(C) C2H5OH, C2H6, C2H5Cl (D) C2H5OH, C2H5 Cl, C2H5ONa
25. Action of alcoholic AgNO3 on chlorobenzene is similar to the action on -

(A) Allyl chloride (B) Vinyl chloride (C) Isopropyl chloride (D) Benzyl chloride
26. The number of steps involved in SN1 and SN2 mechanisms are given by the set -
(A) 1,2 (B) 3,1 (C) 2,1 (D) 2,2
27. Tertiary butyl halide on boiling with water gives tertiary butyl alcohol. The reaction follows -
(A) SE mechanism (B) SNI mechanism (C) SN2 mechanism (D) E1 mechanism
28. Inversion of configuration of the product alcohol during the hydrolysis of an optically active halide is an experimental
evidence for-
(A) SN2 mechanism (B) SNi mechanism (C) SN1 mechanism (D) A carbanion
Alkyl Halide
29. Which one of the following pairs of reaction types included in the reaction sequence below
CH3CH = CHCH3 + HI (in CH3COOH)  CH3CH2CHICH3
CH3CH2CHICH3 + NaOH(aq)  CH3CH2CH(OH)CH3
(A) Electrophilic addition and electrophilic substitution
(B) Electrophilic addition and nucleophilic substitution
(C) Nucleophilic addition and electrophilic substitution
(D) Nucleophilic addition and free radical substitution
30. An alkyl isocyanide is prepared by -

(A) Heating an amide with P2O5 (B) Reacting an alcohol with NH3
(C) The action of AgCN on alkyl halide (D) The action of KCN on alkyl halide

31. CH3Br AgCN
 A H2O B, [B] is -
(A) CH3 NH2 (B) (CH3) NH (C) C2H5 NH2 (D) CH3 COOH
32. Reaction of ethyl bromide and silver acetate gives –

(A) Ethyl ethanoate (B) Methyl ethanoate (C) Ethanoic anhydride (D) 2-Butanone
Chemical Properties & Preparation methods of Diahlides

33. A vicinal dihalide is not formed in the reaction-
(A) HOCH2–CH2OH PBr
3  (B) CH3–CH=CH2 Br

2
HBr
(C) CHCH HBr
 HBr
 (D) CH3–CH=CHBr  
Peroxide
34. 2,2-dichloropropane on hydrolysis yields -

(A) Acetone (B) 2,2-Propane diol (C) Isopropyl alcohol (D) Acetaldehyde
35. Propylidene chloride when heated with zinc gives -

(A) Ethene (B) Propene (C) 1-Butene (D) 3-Hexene
Chemical Properties & Preparation methods of Chloroform

36. CHCl is kept in brown bottles well stoppered and also with 1% alcohol so that it may not form -
3
(A) CH2Cl2 (B) COCl2 (C) CCl4 (D) None of these
37. Chloroform can be obtained from -

(A) Methanol (B) Methanal (C) Propanol–1 (D) Propanol– 2
I H 2SO 4
CH3–C–CH3 
2
(A) Ag   (C)
38. Na 2 CO 3   (B)
powder Hg 
O
Product A, B & C are -

(A) Iodoform, Acetylene & Acetaldehyde
(B) Tri. iodomethane, Ethyne & Acetone
(C) Iodoform, Ethene & Ethylene glycol
(D) Ethene, iodoform & Ethylhydrogen sulphate
Alkyl Halide
39. Which of the following statement is wrong -

(A) All carbonyl compounds of the general structure CH3–C–R give a positive iodoform test
O
(B) All secondary alcohols give iodoform reaction
(C) Alkanols of the structure CH3CH(OH) - R (where R=H, alkyl or aryl) give iodoform reaction.
(D) The only aldehyde giving iodoform reaction is acetaldehyde.
40. The oxidation of CHCl3 by air & light is prevented by adding -

(A) CH3COOH (B) C2H5OH (C) CH3CHO (D) CH3COOCH3
41. Isocyanide reaction involves the intermediate formation of -

(A) :CCl2 (B) CH3+ (C) CH3¯ (D) CCl3
42. Chloroform when treated with aniline and alcoholic KOH forms -
(A) Phenyl cyanide (B) Phenyl isocyanide
(C) Phenyl cyanate (D) Phenyl isocyanate
43. Iodoform test is not given by : -

(A) C6H5COC6H5 (B) CH3COCH3
(C) CH3CH2COCH3 (D) CH3CH2CHOHCH3
44. The compound with no dipole moment is -

(A) Methyl chloride (B) Carbon tetrachloride
(C) Methylene chloride (D) Chloroform
45. The hydrogen atom in chloroform is -

(A) Acidic (B) Basic (C) Neutral (D) None of these
46. Iodoform gives a precipitate with AgNO3 on heating but chloroform does not because -
(A) Iodoform is ionic
(B) Chloroform is covalent
(C) C–I bond in iodoform is weak and C–Cl bond in chloroform is strong
(D) None
47. Pyrene is the commerical name of -

(A) Degreasing agent CHCl3 (B) Fire extinguisher CCl4
(C) Insecticide CHI3 (D) Aerosol, propellant, C2Cl4 F2
Physical properties and test of Alkyl halide

48. The yield of alkyl bromide obtained as a result of heating the dry silver salt of carboxyic acid with bromine what
will be the order of formation w.r.t. alkyl bromide -
(A) 1º > 3º > 2º bromides (B) 1º > 2º > 3º bromides
(C) 3º > 2º > 1º bromides (D) 3º > 1º > 2º bromides
49. True about alkyl halides is/are -

(A) Tertiary alkyl halides undergo SN2 substitutions
(B) Alkyl iodides on exposure to sunlight gradually darken
(C) Alkyl chlorides do not give beilstein test
(D) A nucleophilic substitution is most difficult in alkyl iodides
Alkyl Halide
50. The correct order of density is -

(A) C2H5I > C2H5Br > C2H5Cl (B) C2H5 > C2H5Br > C2H5I
(C) C2H5Cl > C2H5I > C2H5CBr (D) None of these
51. Ethyl bromide and isopropyl chloride can be distinguished by -

(A) Alcoholic AgNO3 (B) Comparing their colours
(C) Burning the compounds on spatula (D) Aqueous KOH solution
52. The compound C2H4Cl2 has two isomers and they can be distinguished by the reaction with
(A) Aq. KOH (B) Alc. KOH (C) Bromine water (D) NaNH2
Alkyl Halide
Exercise - 2 (Level-I) Objective Problems | JEE Main

Prepration of Alkyl halide
1. From each of the following pairs select the compound that will react faster with sodium iodide in acetone
(a) 2-Chloropropane or 2-bromopropane
I II
(b) 1-Bromobutane or 2-bromobutane
I II
(A) (a)-I, (b)-I (B) (a)-I, (b)-II (C) (a)-II, (b)-I (D) (a)-II, (b)-II
O
2.  product are
PCl5
Ph — C — CH3  
Cl
|
(A) Ph — C — CH3 (B) Ph — CH — CH 2
| | |
Cl Cl Cl
Cl
(C) Ph — CH 2 — CH (D) Ph — CH2 — CH2 — Cl
Cl
3. In the acid catalyzed dehydration of alcohols to alkenes, the intermediate species formed is
(A) Free radical (B) Carbocation (C) Carbanion (D) Carbene
Br
H3C H
4. Anti elimination ? major products is :
—Br2
H CH 3
Br
H3C H H3C H
(A) (B)
H CH 3 H3C H
(C) both (A) & (B) (D) none of these
Chemical Reaction of Alkyl Halide
Zn—dust
5. (p)
compound (p) is
CH3 CH3
Br
Br
H Br
(A) (B) H Br
(C) Br (D) Br
H Br Br H
CH3 CH3
Alkyl Halide
CH3
H Br Zn—dust
6. (p). The product (p) is
Br H
CH3
(A) (B) (C) (D)
7. Which of the following compound will be most reactive for SN1 and SN2 reactions
I Cl Br Cl
O O O
(A) (B) (C) (D)
O
CH3 CH 3
8.
Cl
Total number of SN1 products of given compound are
(A) 3 (B) 4 (C) 5 (D) 6
SN2
Nu + C [TS] C + L
9.
Which of the following figures represent correctly the structure of transition state in this reaction?
C C
(A) [ Nu (B) [ Nu
(C) either (A) or (B) depending upon situation (D) none of these
10. Best method for preparation of

CH3
|
CH3— O — C — CH 3 by williamson’s ether synthesis is
|
CH3
CH3
|
(A) CH 3O + CH 3 — C — Br (B) CH 3 — CH — O + CH 3 — CH — Br
| | |
CH3 CH3 CH3
CH 3 CH 3
| |
(C) CH 3 — C — O + CH 3 — Br (D) CH3 — C| — OH + CH3 — Br
|
CH3 CH 3
Alkyl Halide
Br
Zn
11. + ZnBr2
Br
This reaction is a case of
(A) -elimination (B) -elimination (C) -elimination (D) none of these
Br
12.
The major products obtained when this substrate is subjected to E2 reaction will be
(A) (B) (C) both (A) and (B) (D) none of these
13. Which of following cannot undergo an E2 reaction ?

H3C CH2Br H3C Br CH2Br
CH3 CH3
(i) (ii) (iii)
(A) (i) (B) (ii)

(C) (iii) (D) None (all can undergo an E2 reaction)
14. Which alkylbromide will yield-3-methyl-1-hexene as the major product upon treatment with potassium t-butoxide
in t-butyl alcohol (solvent) ?
Br
(A) (B) (C) (D)
Br
Br Br
CH3
15.
Br
CH3
The major product obtained when this substrate is subjected to E2 reaction will be
CH3 CH2
(A) (B) (C) both (A) and (B) (D) none of these
CH 3 CH3
Alkyl Halide
16. If the following E2 reaction proceeds through an anti-periplaner transition state, what products are expected ?
CH 3
Cl
(A) Only 3-methylcyclohexene

(B) Only 1-methylcyclohexene
(C) The major product is 3-methylcyclohexene and the minor product is 1-methyl cyclohexene
(D) The major products is 1-methylcyclohexene and the minor product is 3-methyl cyclohexene
alc. KOH
17. CH 3 — CH2 — CH — CH 3
Br
X EtONa Y
;
Major CH 3 — CH2 — CH — CH 3 Major
NMe3
+
Product (X) and (Y) respectively is

(A) 1-butene, trans-2-butene
(B) 1-butene, cis-2-butene
(C) cis-2-butene, 1-butene
(D) trans-2-butene, 1-butene
CH 3
18.
Br
CH3
The major product obtained when this substrate is subjected to E1 reaction will be
CH 3 CH3 CH 3
(A) (B) (C) (D) none of these

CH2 CH3 CH3
Alkyl Halide
Exercise - 2 (Level-II) Multiple Correct | JEE Advanced

Comprehension (Q.1 to 7)
(A) Cl (B) Cl
(C) Cl (D) CH3–Cl
1. Most reactive towards SN1 reaction

2. Most reactive towards SN2 reaction ?
3. Most reactive towards E2 reaction ?
4. Most reactive towards E1 reaction ?
5. Consider the given reaction
CH3
| NaCN
H — C — OTs CH3CH2CH—CN
| |
(S)
C2H5 CH3
Which of following statement are correct for above reaction.
(A) Product formation takes place due to the breaking of O— Ts
(B) The reaction SN2
(C) The reaction is SN1
(D) Configuration of product is (R)
6. Which are possible products in following

CH 3 moist Ag2O
CH 2Cl SN1
CH3 OH CH2OH CH3

| |
CH3
(A) CH2OH
(B) (C) (D)
OH
7. SN1 & SN2 product are same in (excluding steroisomer)
Cl
H
(A) (B) (C) (D) Ph — CH — CH — CH 3
| |
Cl CH3 Cl
Cl
Paragraph for Question Nos. 8 to 10

(3 questions) :
Dehydration require an acid catalyst to protonate the hydroxy group of the alcohol and convert it into good leaving
group. Loss of water followed by a loss of a proton, given the alkene an equilibrium is stablished between
reactants and products.
OH
+
H
CH 3—CH=CH 2
Alkyl Halide
Mechanism
H
+ +
OH + H2SO4 O CH3—CH—CH 2
(r.d.s) |
HSO4
H H
H2O:
+
CH 3—CH=CH2 + H 3O
8. To improve the yield of above reaction which of following is correct.

(A) High temperature (B) Distillation (C) Addition of H2O (D) Both (A) and (B)
+
H OH +
H
9. (i) (A) Major (ii) (B) Major
OH
OH
+
H
(C) Major
Total number of -hydrogen in A + B + C is

(A) 23 (B) 25 (C) 37 (D) 29
10. Which alcohol is most reactive towards dehydration of alcohols in acids catayzed reaction.
OH OH
(A) (B)
OH
OH
(C) (D)
Matrix Match
11. Column I Column II
Primary alkyl bromide SN2 relative rate
(A) CH3 — CH2 — Br (P) 10–5
(B) Me — CH2 — CH2 — Br (Q) 10–2
(C) Me — CH — CH 2 — Br (R) 0.8
|
Me
Me
|
(D) Me — C — CH2 — Br (S) 1
|
Me
Alkyl Halide
12. Column I Column II

Alkyl—P—toluene sulfonate Ethanolysis relative
(A) CH3 — CH2 — OTs (P)1010
(B) H2C = CH — CH2 — OTs (Q) 105
(C) Ph — CH2 — OTs. (R) 400
(D) Ph — CH — OTs (S) 35
|
Ph
(E) Ph3C — OTs. (T) 1
13. Substrate E2 elimination SN2 — substitution

(A) CH3 – CH2 – Br (P) 1 (W)  0
(B) (CH3)2CH – Br (Q) 80 (X) 20
(C) (CH3)3CBr (R) 100 (Y) 90
14. Reaction Reaction rate of reaction
(A) HO + R — CH2 — I  (P) 1
(B) HO + R — CH2 — Br  (Q) 200
(C) HO + R — CH 2 — Cl  (R) 10,000
(D) HO + R — CH2 — F  (S) 30,000
15. column I Column II

Alkyl-bromide Relat ive r at e of SN1
CH3
|
(A) CH3 — C — Br (P) 1
|
CH3
(B) CH 3 — CH — Br (Q) 11.6

|
CH3
(C) CH3 — CH2 — Br (R) 1,200,000
16. column I Column II

Solvent Relative rate of SN1
(A) 100% water (P) 1200
(B) 80% water + 20% ethanol (Q) 400
(C) 50% water + 50% ethanol (R) 60
(D) 20% water + 80% ethanol (S) 10
(E) 100% ethanol (T) 1
17. Match List-I with List II for given SN2 reaction & select the correct answer from the codes given below
Z—CH 2Br + CH 3O  Z—CH 2OCH3 + Br

List I List II (relative reactivity)
(A) H— (P) 0.1
(B) CH3— (Q) 3
(C) C2H5— (R) 1
CH 3
(D) CH— (S) 100
CH3
Alkyl Halide
Exercise - 3 | Subjective | JEE Advanced

1. Which of the following reaction is not possible
(A) R – OH + NaBr  R – Br + NaOH (B) R – OH + HBr R – Br + H2O
(C) both reaction are possible (D) both reactions are not possible
2. Which of the following compound will not undergo acid catalysed hydrolysis ?
O—CH 3 O—Ph O—CH2CH3
O
(A) (B) (C) (D)
Br
Br Br
3.
II III
I
SN2 reactivity of these substrate, under identical conditions, will be in the order as
(A) I > II > III (B) III > II > I (C) III > I > II (D) II > III > I
4. A gem dichloride is formed in the reaction except
(A) CH3CHO and PCl5 (B) CH3COCH3 and PCl5
OH O
2PCl5
(C) (D) PCl 5
OH
5. Which of the following nucleophile will show minimum reactivity towards SN2 reaction
H
(A) Me3CO (B) MeO (C) (D) Me2CHO
O
6. Which of following compounds will show NGP ?
Cl
H H
(A) SPh H (B) H H (C) (D)
Cl
H Cl PhS Cl
OCH3
(x) conc. HI
7.
OCH 3
Value of x in above reaction is

(A) 2 (B) 3 (C) 4 (D) 5
Alkyl Halide
OCH3
( X) Conc.HI
8.    
OCH3
x = moles of HI consumed
value of x is
(A) 2 (B) 4 (C) 5 (D) 6
9. Consider the reaction of HI with the following
O
I II
O
Which forms di-iodide on reaction with HI(excess)?
(A) I and II both (B) II only (C) I only (D) none
CH3 CH 3
EtOH
10. Ph – CH — C — CH3 (A)
(SN1)
Br
Major-product (A) is
CH3 CH 3 CH3 CH3
(A) Ph – CH – C – CH3 (B) Ph – C — CH — CH3

OEt OEt
OEt CH3
Ph CH3
(C) (D) Ph – C — C — CH3
CH3 CH3
H CH3
CH3
SOCl2
11. H OH (A) . Product (A) in
Et
CH3 Et CH 3
(A) H Cl (B) H Cl (C) Cl H (D)
Et CH3 Et
H 3O
12. CH3 – CH 2 – O – C = CH2 Products are
CH 3
O
O
(A) + EtOH (B) + EtOH
OH
OH
(C) + EtOH (D) + O
Alkyl Halide
H3O
excess X
13.
O O
Structure of X is
(A) (B)
HO HO H O OH H O OH
(C) (D)
OH HO HO HO
O OH
14. In the given reaction :
Cl
Cl
CH 3OH
[X]
O Cl
Cl OCH3 Cl OCH3
Cl Cl OCH3 Cl
(A) (B) (C) (D)
O OCH 3 O OCH 3 O Cl O Cl
15. Among the bromides I-III given below, the order of reactivity is SN1 reaction is
(I) (II) (III)
Br Br
Br
(A) III > I > II (B) III > II > I (C) II > III > I (D) II > I > III
CH2 — OH
(x)HBr
16.
OH
Value of (x) is
(A) 1 (B) 2 (C) 3 (D) 4
Alkyl Halide
(i) SH (one equivalent)

17. In the given reaction CH3 — CH — CH2 — CH2 — CH — CH3 [X] , [X] will be :
| | (ii) KOH
OTs OTs
OTs S S S
| | | |
(A) CH3 — CH — CH2 — CH2 — CH — CH3 (B) CH3 — CH — CH2 — CH2 — CH — CH3
CH3 CH3
S
CH3 CH3
(C) (D) S
+
H
18. (B) , Give structure of (B)
(A) (B) O (C) (D)
t-Bu +
OTs AcO Na
19. (A)
Major-product (A) is
OAc
(A) t-Bu (B) t-Bu

OAc
(C) t-Bu (D) t-Bu

OAc
Br
| (x) NaNH2 +
20. Ph — CH — CH 2
|
Br (x = No. of moles of NaNH2)
Value of x is
(A) 1 (B) 2 (C) 3 (D) 4
Alkyl Halide
21. The energy profile of the given reactions.
+ + +
H —H
CH3 — CH — CH3 CH3 — CH — CH3 CH3 — CH — CH3 CH3 — CH = CH2
| +|
OH O
H H
(A) E (B) E (C) E (D)

E
rxn-coordinate rxn-coordinate rxn-coordinate

rxn-coordinate
CH3
+
CH 3 H
22. (x)
OH
Major product (X) is
CH 3
(A) (B) (C) (D)

CH 3
23. Which of the following alcohols would be most likely to undergo dehydration with rearragement by a process
involving a methyl migration (methyl shift only) ?
OH
(A) (B) (C) (D)
OH OH OH
OH
H2SO4
24. X, X is
OH
OH OH O
(A) (B) (C) (D)
OH
25. Rate of dehydration when given compound is treated with conc. H2SO4.
OH OH
CH 2OH OH CH
CH 3 3 CH 3
(P) (Q) (R) (S)
(A) P > Q > R > S (B) Q > P > R > S (C) R > Q > P > S (D) R > Q > S > P
Alkyl Halide
conc. H2SO4
26. HO OH A
OH
Final product A is
(A) HO O (B) CH2 = C = CH2
(C) (D) HO
O O
Me
conc. H2SO4
27. Me A.
OH OH
Product A is
Me Me
Me Me
(A) (B) (C) (D) Me
Me Me C—Me
O O
O
Me
H Et alc. KOH
28. major product is :
Br Et
Me
Me Me Me Et
(A) (B)
Et Et Et Me
Me Me
H Et H Et
(C) (D)
Me
29. Most reactive towards acid-catalyzed hydrolysis is

OEt
(A) (B) OEt (C) EtOEt (D) EtOH
OEt
Br
|
30. —C — CH2 — CH3
|
CH2 — CH2 — CH3
Total number of products obtained when this substrate is subjected to E2 reaction will be (including streoisomer)
(A) 3 (B) 4 (C) 5 (D) 6
Alkyl Halide
CH3
Br
31. CH3
The major products obtained when this substrate to E2 reaction under the treatment of potassium tert-butoxide
will be
CH2 CH3
(A) (B)
CH3 CH3
(C) both in equal proportions (D) none of these
CH 3 CH3 CH3
32. I II III
Br Br
Br
CH3
Ease of -dehydrobromination among these substrates under the treatment of strong base will be in the order as
(A) i > ii > iii (B) iii > ii > i (C) ii > i > iii (D) ii > iii > i
CH3OH
33. CH3O — CH = CH2 product formed is
H+
(A) Acetal (B) Hemiacetal (C) Alcohol (D) aldehyde
Br
34. CH3 — CH2 — CH2 — C — CH2 — CH3
CH3
Total number of SN1 + E1 products obtained will be -

(A) 5 (B) 6 (C) 7 (D) 8
CH3
+
35. CH3 — C — CH2 — CH3 H
CH3 OH
+ OH +
(A) H (B) H (C)
OH
Stability of product (A), (B), (C) is :

(A) C > B > A (B) A > B > C (C) B > C > A (D) C > A > B
Alkyl Halide
36. Which of the following isomeric hexchlorocyclohexanes is least reactive in ()-dehydrochlorination of treatment
with strong base
Cl Cl Cl
Cl Cl Cl Cl Cl Cl
(A) (B) (C)

Cl Cl Cl Cl Cl Cl
Cl Cl
Cl
(D) all three are equally reactive
37. The nitrogen atom in each of the following tertiary amines may be removed as trimethyl amine by repeated
Hofmann eliminations (exhaustive methylation followed by heating with AgOH).
Which of the amines requires the greater number of Hofmann sequences to accomplish this ?
CH3 N(CH3)2 CH3

N N
(A) (B) (C) (D)
N
Br CH3
– SN2
38. + OH A , A is
H H
HO H H HO CH 3
CH 3
(A) (B) (C) both (D)
H CH3 OH H H
H
18
O—CH3
Conc. HI
39. Product are
18
OH I OH I
18
(A) + CH3I (B) + CH3OH (C) + CH3I (D) + H2O
alc. KOH
40. CH3 — CH2 — CH — CH3 X (Major)
|
Br
(A) (B) (C) (D) None of these
Alkyl Halide
41. Among the given compounds, the correct dehydration order is :
(i) OH (ii) OH (iii) OH (iv) OH
(A) i < ii < iii < iv (B) ii < iii < iv < i (C) i < iii < iv < ii (D) i < ii < iii = iv
Ph Ph
C—C
Conc. H2SO4
42. OH OH A, A is :
MeO CH3
Ph Ph
Ph Ph
C=C
(A) (B) MeO C– C=O
MeO CH3
CH3
Ph Ph O
(C) CH3 C — C — Ph (D) Ph — C — C Me
O
OMe
43. Which of the following expressions is the experimentally observed rate law for an E2 reaction of alkyl halide ?
(A) Rate = k[RX] (B) Rate = k [RX]2 (C) Rate = k[RX][base] (D)Rate = k[base]
Alkyl Halide
Exercise - 4 | Level-I Previous Year | JEE Main

Q.1 The correct order of the thermal stability of hydrogen halides (H – X) is – [AIEEE-2005]
(A) HF > HCl > HBr > HI (B) HI > HBr > HCl > HF
(C) HI > HCl < HF > HBr (D)HCl < HBr > HBr < HI
Q.2 Tertiary alkyl halides are practically inert to substitution by SN2 mechanism because of – [AIEEE-2005]
(A) instability (B) insolubility (C) steric hindrance (D) inductive effect
Q.3 Alkyl halides react with dialkyl copper reagents to give [AIEEE-2005]
(A) alkyl copper halides (B) alkenes
(C) alkenyl halides (D) alkanes
Q.4 Elimination of bromine from 2–bromobutane results in the formation of – [AIEEE-2005]

(A) predominantly 2–butene (B) equimolar mixture of 1 and 2–butene
(C) predominantly 2–butyne (D) predominantly 1–butene
Q.5 Among the following the one that gives positive iodoform upon reaction with I2 and NaOH is –[AIEEE 2006]
(A) C6H5 CH2CH2OH (B)

(C) PhCHOHCH3 (D) CH3 CH2CH(OH)CH2CH3
Q.6 Which of the following is the correct order of decreasing SN2 reactivity ? [AIEEE 2007]
(A) RCH2X > R3CX > R2CHX (B) RCH2X > R2CHX > R3CX
(C) R3CX > R2CHX > RCH2X (D) R2CHX > R3CX > RCH2X
(X = a halogen)
Q.7 The organic chloro compound, which shows complete stereochemical inversion during a SN2 reaction , is
[AIEEE 2008]
(A) (CH3)3CCl (B) (CH3)2CHCl (C) CH3Cl (D) (C2H5)2CHCl
Q.8 Which of the following on heating with aqueous KOH, produces acetaldehyde ? [AIEEE 2009]
(A) CH3COCl (B CH3CH2Cl (C) CH2Cl CH2Cl (D) CH3CHCl2
Q.9 Consider the following bromides : [AIEEE 2010]

Me
Me
Me
(i) Me (ii) (iii)
Br
Br Br
The correct order of SN1 reactivity is
(A) (ii) > (iii) > (i) (B) (ii) > (i) > (iii) (C) (iii) > (ii) > (i) (D) (i) > (ii) > (iii)
10. Which branched chain isomer of the hydrocarbon with molecular mass 72u gives only one isomer of mono
substituted alkyl halide ? [JEE Main 2012]
(A) Isohexane (B) Neohexane
(C) Tertiary butyl chloride. (D) Neopentane
11. Iodoform can be prepared from all except : [JEE Main 2012]
(A) 3 - Methyl - 2 - butanone (B) Isobutyl alcohol
(C) Ethyl methyl ketone (D) Isopropyl alcohol
12. What is DDT among the following [JEE Main 2012]

(A) Biodegradable pollutant (B) Non-biodegradable possutant
(C) Greenhouse gas (D) A fertilizer
Alkyl Halide
13. Compound (A), C8H9Br, gives a white precipitate when warmed with alcoholic AgNO3. Oxidation of (A) gives
an acid (B), C8H6O4. (B) easily forms anhydride on heating. identify the compound (A). [JEE Main 2013]
CH2Br
CH2Br
CH2Br C2H5
(A) (B) (c) (D)

CH3 CH3 Br
CH3
14. A solution of (–) –1–chloro–1-phenylethane in toluene racemizes slowly in the presence of a small amount of
SbCl5. due to formation of : [JEE Main 2013]
(A) carbocation (B) free radical (C) carbanion (D) carbene
15. In SN2 reactions, the correct order of reactivity for the following compounds ? [JEE Main 2014]
CH3Cl, CH3CH2Cl, (CH3)2CHCl and (CH3)3CCl is
(A) CH3CH2Cl > CH3Cl > (CH3)2CHCl > (CH3)3CCl
(B) (CH3)2CHCl > CH3CH2Cl > CH3Cl > (CH3)3CCl
(C) CH3Cl > (CH3)2CHCl > CH3CH2Cl > (CH3)3CCl
(D) CH3Cl> CH3CH2Cl > (CH3)2CHCl > (CH3)3CCl
16. The synthesis of alkyl fluorides is best accomplished by : [JEE Main 2015]
(A) Free radical fluorination (B) Sandmeyer's reaction
(C) Finkelstein reaction (D) Swarts reaction
17. The major product obtained in the following reaction is : [JEE Main 2017]
Br
H
tBuOK
C6H5
C6H5 (+)
(A) C6H5CH = CHC6H5 (B) (+)C6H5CH(OtBu) CH2C6H5
(C) (–)C6H5CH(OtBu)CH 2C6H5 (D) (±)C6H5CH(OtBu)CH 2C6H5
18. The increasing order of the reactivity of the following halides for the SN1 reaction is : [JEE Main 2017]
CH3CHCH2CH3 CH3CH2CH2Cl p-H3CO–C6H4–CH 2Cl
Cl
(I) (II) (III)
(A) (II) < (I) < (III) (B) (I) < (III) < (II)
(C) (II) < (III) < (I) (D) (III) < (II) < (I)
19. Which of the following, upon treatment with tert-BuONa followed by addition of bromine water, fails to decolourize
the colour of bromine ? [JEE Main 2017]
O
C6H 5 O O
(A) (B) (C) (D)
Br Br Br Br
20. The major product formed in the following reaction is: [JEE Main 2018]
I OH I OH
(A) (B) (C) (D)
OH OH I I
Alkyl Halide
21. The major product of the following reaction is : [JEE-Mains-2018]
Br NaOMe
MeOH
OMe OMe
(A) (B) (C) (D)
22. The major product of the following reaction is : [JEE-Mains Online -2019]
(i) KOH (alc.)

(2) Free radical
Cl Cl polymerisation
CH3 CH3
n n
n
n
(A) (B) (C) (D)

Cl
OH
OH Cl
23. Increasing order of reactivity of the following compunds for SN1 substitution is : [JEE-Mains Online -2019]
CH3
CH2 – Cl Cl Cl
H3C Cl
CH3
H3CO
(i) (ii) (iii) (iv)
(A) (ii) < (i) < (iv) < (iii) (B) (ii) < (iii) < (i) < (iv)
(C) (i) < (ii) < (iv) < (iii) (D) (ii) < (iii) < (iv) < (i)
24. Heating of 2-chloro-1 phenylbutane with EtOK/EtOH gives X as the major product. Reaction of X with Hg
(OAc)2/H2O followed by NaBH4 gives Y as the major product . Y is : [JEE-Mains Online -2019]
OH OH
(A) Ph (B) Ph (C) Ph (D) Ph

OH
Br
KOH alc (excess)

Ph
Br
(A) (B) (C) (D)

Ph Ph
Ph Ph
Alkyl Halide
26. Which of the following compounds will show retention in configuration on nucleophile substitution by ion ?
[JEE-Mains Online -2020]
(A) (B) (C) (D)
27. The major aromatic product C in the following reaction sequence will be :
[JEE-Mains Online -2020]
(A) (B) (C) (D)
28. The major product obtained from E2-elimination of 3-bromo-2- fluoropentane is [JEE-Mains Online -2020]
CH3 CH3
| |
(A) CH3—CHz—C——CH—CH3 — CH3
(B) CH3CH2—CH—CH—
CH3
|
(C) CH 3—CH —
— CH—CH—CH 3 (D) CH3CH2CH —
—C—F
|
CH3
29. The mechanism of SN1 reaction is given as: [JEE-Mains Online -2020]
R—X R  X R|| X Y R — Y + X
Ion pair Solvent
Separated ion
pair
A student writes general characteristics based on the given mechanism as :

(a) The reaction is favoured by weak nucleophiles.
(b) R would be easily formed if the substituents are bulky
(c) The reaction is accompanied by racemization
(d) The reaction is favoured by non-polar solvents.
Which observations are correct ?
(A) (b) and (d) (B) (a) and (c) (C) (a) and (b) (D) (a), (b) and (c)
30. The decreasing order of reactivity of the following compounds towards nucleophilic substitution (S N2)
is : [JEE-Mains Online -2020]
(A) (II) > (III) > (I) > (IV) (B) (II) > (III) > (IV) > (I)
(C) (III) > (II) > (IV) > (I) (D) (IV) > (II) > (III) >(I)
Alkyl Halide
31. When neopentyl alcohol is heated with an acid, it slowly converted into an 85 : 15 mixture of alkenes A and B,
respectively. What are these alkenes ? [JEE-Mains Online -2020]
(A) (B)
(C) (D)
32. Consider the reaction sequence given below : [JEE-Mains Online -2020]
Which of the following statements is true:

(A) Changing the concentration of base will have no effect on reaction (A)
(B) Doubling the concentration of base will double the rate of both the reactions
(C) Changing the concentration of base will have no effect on reaction (B)
(D) OH will have no effect on reaction (B)
33. The major product [B] in the following reaction is : [JEE-Mains Online -2020]
(A) CH2 = CH2 (B)
(C) (D) CH3 – CH2CH = CH – CH3
34. The major product [R] in the following sequence of reaction is : [JEE-Mains Online -2020]
H3C
H3C
(A) C = CH– CH3 (B) CH – CH= CH2
(CH3)2CH (CH3)2CH
H2C H3C
(C) C – CH2– CH3 (D) C = C(CH3)2
CH(CH3)2 H3CCH2
Alkyl Halide
35. The major product in the following reaction is : [JEE-Mains Online -2020]
CH3CH = CHCH(CH3)2 HBr

(A) CH3CH(Br)CH 2CH(CH3) 2 (B) Br(CH 2) 3CH(CH 3) 2
(C) CH3CH2CH2C(Br)(CH 3) 2 (D) CH3CH2CH(Br)CH(CH 3) 2
OH CH2CH3
H2SO4
CHCH3 CH2CH3 CH2CH 3 CH = CH2
(A) (B) (C) (D)

O O O O
37. The major products of the following reaction are : [JEE-Mains Online -2020]
CH3 CH3
(A) + CH3CHO (B) + HCHO

H3C O H3C CHO
CH3 CH3
(C) + CH3COOH (D)

+ HCOOH
H3C H3C COOH
O
38. The major product in the following reaction is: [JEE-Mains Online -2020]
(A) (B) (C) (D)
39. The correct order of the following compounds showing increasing tendency towards nucleophilic substitution
reaction is : [JEE-Mains (24-Feb_Shift -2)2021]
Cl Cl Cl Cl
NO2 O2N NO2
NO2 NO2 NO2

(iii) (iv)
(i) (ii)
(A) (iv) < (i) < (iii) < (ii) (B) (iv) < (i) < (ii) < (iii)
(C) (i) < (ii) < (iii) < (iv) (D) (iv) < (iii) < (ii) < (i)
Alkyl Halide
40. The total number of amines among the following which can be synthesized by Gabriel synthesis is _______.
[JEE-Mains (24-Feb_Shift -2)2021]
CH 3 CH–CH 2–NH 2
(A) (B) CH3CH2NH2
CH3
CH2 –NH 2 NH2

(C) (D)
41. Identify A and B in the chemical reaction. [JEE-Mains (25-Feb_Shift -1)2021]
OCH 3
 A (Major)  
 B (Major)
NaI

HCl
dry acetone
NO2
OCH 3 I OCH 3 I
Cl Cl
A= B= A= B=
(A) (B)
Cl Cl
NO2 NO2 NO2 NO2
OCH 3 OCH 3 OCH 3 OCH3

Cl Cl I
A= B= A= B=
(C) (D)
Cl
NO2 NO2 NO2 NO2
42. Match List-I with List-II [JEE-Mains (26-Feb_Shift -2)2021]

List-I List-II
Cl
N2+ Cl–
(a)  
Cu2Cl2
 +N2 (i) Wurtz reaction
Cl
N2 +Cl–
(b)  
Cu,HCl
 +N2 (ii) Sandmeyer reaction
(c) 2CH3CH2Cl + 2Na  

Ether
 C2H5– C2H5 + 2NaCl (iii) Fitting reaction
(d) 2C2H5Cl +2Na  
Ether
 C6H5– C6H5 + 2NaCl (iv) Gatterman reaction
Choose the correct answer from the option given below:
(A) (a)-(ii), (b)-(i), (c)-(iv), (d)-(iii) (B) (a)-(iii), (b)-(iv), (c)-(i), (d)-(ii)
(C) (a)-(ii), (b)-(iv), (c)-(i), (d)-(iii) (D) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii)
Alkyl Halide
43. Identify A in the given reaction [JEE-Mains (26-Feb_Shift -2)2021]
OH
SOCl 2
A (Major product)
HO CH2 OH
OH OH Cl
Cl
(A) (B) (C) (D)
OH CH2 Cl Cl CH2 Cl OH CH2 OH

Cl CH2 Cl
44. For the given reaction : [JEE-Mains (26-Feb_Shift -1)2021]
CH 2CH3
Br
 2
UV light
 'A'
(major product)
monobrominated
CN
What is ‘A’ ?
CH2 CH 3 Br CH3
CH2CH3 CH 2CH3 CH
Br
(A) (B) (C) (D)
CN
Br CN
Br CN CN
45. For the given reaction : [JEE-Mains (26-Feb_Shift -1)2021]
CH CHBr
1. NaNH
2.Red 2
 hot
      
iron tube, 873 K
(A)
(major product)
CH3
What is ‘A’
H3C CH 3
(A) CH = CH– NH2 (B) (C) (D) CH3CH2CH2NH2
CH3
CH3
Alkyl Halide
46. Given below are two statements : [JEE-Mains (18-March_Shift -1)2021]
Statement I : C2H5OH and AgCN both can general nucleophile.
Statement II : KCN and AgCN both will generate nitrile nucleophile with all reaction condition.
Choose the most appropriate option:
(A) Statement I is false but statement II is true.
(B) Statement I is true but statement II is false.
(C) Both statement I and statement II are false.
(D) Both statement I and statement II are true.
H3C OH H3 C Cl
47. 20 % H3PO4 (CH3)3CO–K +
"A" "B"
358 K
(Major Product) (Major Product)
The products “A” and “B” formed in above reactions are: [JEE-Mains (16-March_Shift -1)2021]
CH3 CH2 CH 2 CH 3
(A) A– B– (B) A– B–
CH2 CH2 CH3 CH3
(C) A– B– (D) A– B–
Cl
A
48. [JEE-Mains (16-March_Shift -2)2021]
Cl
Identify the reagent(s) ‘A’ and condition(s) for the reaction

(A) A = HCl; Anhydrous AlCl3 (B) A = HCl, ZnCl2
(C) A = Cl2, dark, Anhydrous AlCl3 (D) A = Cl2; UV light
49. Ammonolysis of Alkylhalides followed by the treatment with NaOH solution can be used to prepare primary,
secondary and tertiary amines. The purpose of NaOH in the reaction is :
(A) to remove basic impurities [JEE-Mains (16-March_Shift -2)2021]
(B) to activate NH3used in the reaction
(C) to increase the reactivity of alkyl halide
(D) to remove acidic impurities
Alkyl Halide
Cl O–Na+
50. [JEE-Mains (17-March_Shift -1)2021]

+ NaOH
The above reaction requires which of the following reaction conditions?

(A) 623 K, 300 atm (B) 573 K, 300 atm
(C) 573 K, Cu, 300 atm (D) 623 K, Cu 300 atm
51. Which of the following reaction is an example of ammonolysis ?

(A) C6H5CH2CN  [ H]
 C6H5CH2CH2NH2 [JEE-Mains (17-March_Shift -1)2021]
(B) C6H5COCl + C6H5NH2 C6H5CONHC6H5
(C) C6H5CH2Cl + NH3 C6H5CH2NH2

(D) C6H5NH2 HCl
 C6 H 5 N H 3Cl –
52. The correct pair(s) of the ambident nucleophiles is (are) : [JEE-Mains (17-March_Shift -2)2021]
(A) AgCN/KCN
(B) RCOOAg/RCOOK
(C) AgNO2/KNO2
(D) AgI/KI
(A) (A) and (C) only (B) (B) only
(C) (B) and (C) only (D) (A) only
53. Match List-I with List-II : [JEE-Mains (18-March_Shift -1)2021]

List-I List-II
(Chemicals) (Use/Preparation/Constituent)
(a) Alcoholic potassium hydroxide (i) electrodes in batteries
(b) Pd/BaSo4 (ii) obtained by addition reaction
(c)BHC (Benzene hexachloride) (iii) used for -elimination reaction
(d) Polyacetylene (iv) Lindlar’s Catalyst
Choose the most appropriate match :
(A) (a)-(ii), (b)-(i), (c)-(iv), (d)-(iii) (B) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii)
(C) (a)-(ii), (b)-(iv), (c)-(i), (d)-(iii) (D) (a)-(iii), (b)-(iv), (c)-(ii), (d)-(i)
Alkyl Halide
Exercise - 4 | Level-II Previous Year | JEE Advanced

1. The following compound on hydrolysis in aqueous acetone will give : [IIT 2005]
CH 3 CH3 CH 3
CH 3 CH3 CH 3
NO 2
(K) NO 2 (L)
H Cl CH 3
H OH CH 3
CH 3 CH3 CH 3 CH 3 CH3 CH 3
NO 2 (M) NO 2
OH H CH 3 H CH3 OH
(A) mixture of (K) and (L) (B) mixture of (K) and (M)
(C) only (M) (D) Only (K)
2. Cyclohexene is best prepared from cyclohexanol by which of the following [IIT ‘2005]
(A) conc. H3PO4 (B) conc. HCl/ZnCl2 (C) conc. HCl (D) Conc. HBr
3. 1–bromo–3–chlorocyclobutane when treated with two equivalents of Na, in the presence of ether which of the
following will be formed? [IIT ‘2005]
(A) (B) (C) (D)
 (i) O
H ,
4.   X   3   Y. [IIT 2005]
(ii) Zn / CH3COOH
Identify X and Y.
5. Match the following : [IIT 2006]

Column I
(A) CH3—CHBr—CD3 on treatment with alc. KOH gives CH2 = CH — CD3 as a major product
(B) Ph—CHBr—CH3 reacts faster than Ph—CHBr—CD3.
(C) Ph—CH2—CH2Br on treatment with C2H5OD/C2H5O— gives Ph—CD = CH2 as the product.
(D) PhCH2CH2Br and PhCD2CH2Br react with same rate
Column II
(P) E1 reaction
KOH gives CH2 = CH — CD3 as a major product (Q) E2 reaction
(R) E1 cb reaction gives Ph—CD = CH2 as the product.
(S) First order reaction
6. The reagent(s) for the following conversion.

Br ?
H H is/are [IIT 2007]
Br
(A) alcoholic KOH
(B) alcoholic KOH followed by NaNH2
(C) aqueous KOH followed by NaNH2 (D) Zn/CH3OH
7. The number of stereoisomers obtained by bromination of trans-2-butene is [IIT 2007]

(A) 1 (B) 2 (C) 3 (D) 4
Alkyl Halide
8. The major product of the following reaction is [IIT 2008]
Me Br
F
 
Ph S N a
    
dim ethyl formamide
NO2
Me SPh Me SPh Me Br Me SPh
F F SPh SPh
(A) (B) (C) (D)
NO2 NO2 NO2 NO2
9. The correct stability order for the following species is [IIT ‘2008]
O O
(I) (II) (III) (IV)
(A) II > IV > I > III (B) I > II > III > IV (C) II > I > IV > III (D) I > III > II > IV
10. In the following carbocation, H/CH3 that is most likely to migrate positively charged carbon is [IIT 2009]
H H
1 2 + 4 5
H3C – C – C – C – CH3
HO H CH3
(A) CH3 at C-4 (B) H at C-4 (C) CH3 at C-2 (D) H at C-2
11. The synthesis of 3-octyne is achieved by adding a bromoalkane into a mixture of sodium amide and an alkyne.
The bromoalkane and alkyne respectively are – [IIT 2010]
(A) BrCH 2CH2CH2CH2CH3 and CH3CH2CCH
(B) BrCH2CH2CH3 and CH3CH2CH2CCH
(C) BrCH2CH2CH2CH2CH3 and CH3CCH
(D) BrCH2CH2CH2CH3 and CH3CH2CCH
12. The bond energy (in kcal mol–1) of a C – C single bond is approximately [IIT 2010]
(A) 1 (B) 10 (C) 100 (D) 1000
13. The major product

O of the following reaction is : [IIT 2011]
C
(i) KOH
NH
C
(ii) Br CH 2Cl
O
Alkyl Halide
O O
C C
(A) N—CH2 Br (B) N CH 2Cl
C C
O O
O O
C C
(C) N (D) N
C C
O — CH2 Br O CH2Cl
14. The total number of alkenes possible by dehydrobromination of 3-bromo-3-cyclopentylhexane using alcoholic
KOH is : [IIT 2011]
15. The major product of the following reaction is [IIT 2011]
RCH2OH
+
H (anhydrous)
O
(A) a hemiacetal (B) an acetal (C) an ether (D) an ester
16. KI in acetone, undergoes SN2 reaction with each of P,Q,R and S. The rates of the reaction vary as.
O
H3C—Cl Cl
Cl
[JEE Adv. 2013]
(A) P>Q>R>S (B) S>P>R>Q (C) P>R>Q>S (D) R>P>S>Q
17. The reactivity of compound Z with different halogens under appropriate conditions is given below :
mono halo substituted derivative when X2 = l2

OH
X2
di halo substituted derivative when X2 = Br2
C(CH3)3 [JEE Adv. 2014]
Z
Tri halo substituted derivative when X2 = Cl 2
The observed pattern of electrophilic substitution can be explaind by :

(A) the steric effect of the halogen
(B) the steric effect of the tert-butyl group
(C) the electronic effect of the phenolic group
(D) the electronic effect of the tert-butyl group
Alkyl Halide
18. In the following monobromination reaction, the number of possible chiral products is: [JEE Adv. 2016]
CH2CH2CH3
Br2(1.0 mole)
H Br
CH3 300°C
(1.0 mole)
(enantiomerically pure)
19. For the following compounds, the correct statement(s) with respect to nucleophilic substitution reactions is (are)
[JEE Adv. 2017]
CH 3 CH3
Br Br H 3C—C—Br Br
CH 3
(I) (II) (III) (IV)
(A) I and II follow SN2 mechanism
(B) Compound IV undergoes iniversion of configuration
(C) The order of reactivity for I, III and IV is : IV > I > III
(D) I and III follows SN1 mechanism
20. In the following reaction sequence, the correct structure(s) of X is (are) [JEE Adv. 2018]
Me N3
(1) PBr3, Et2O
X
(2) NaI, Me2CO
(3) NaN3, HCONMe2
enantiomerically pure
Me OH Me OH
(A) (B) (C) (D)
Me OH Me OH
Alkyl Halide
21. LIST-I contains reactions and LIST-II contains major products. [JEE Adv. 2018]
LIST-I LIST-II
P. + 1.
ONa Br OH
Q. + HBr 2.
OMe Br
R. + NaOMe 3.
Br OMe
S. + MeBr 4.
ONa
O
5.
Match each reaction in LIST-I with one or more product in LIST-Il and choose the correct option.
(A) P  1, 5; Q  2; R  3; S  4 (B) P  1, 4; Q  2; R  4; S  3
(C) P  1, 4; Q  1, 2; R  3, 4; S  4 (D) P  4, 5; Q  4; R  4; S  3, 4
22. Choose the correct option(s) for the following set of reactions [JEE Adv. 2019]
(i) MeMgBr conc. HCl S

C6H 10O Q
(ii) H 2o (major)
20% H3PO4, 360 K
(i) H2, Ni HBr, benzoyl peroxide

T R U
(major) (ii) Br2, hv (major)
(major)
H3C Cl CH3 CH3 H3C Br

Br Br
(A) (B)
S U U T
CH3 H3C Br H3C Br CH3

Cl Cl
(C) (D)
S T U S
23. Which of the following plots is(are) correct for the given reaction ? [JEE Advance 2020]
([P]0 is the initial concentration of P)
+ NaOH + NaBr
P Q
(A) (B) (C) (D)
Alkyl Halide
1. D 2. D 3. C 4. A 5. B 6. C 7. C
8. B 9. C 10. D 11. B 12. D 13. B 14. C.
15. B 16. D 17. D 18. A 19. A 20. B 21. B

22. B 23. B 24. A 25. B 26. C 27. B 28. A
29. B 30. C 31. A 32. A 33. C 34. A 35. D
36. B 37. D 38. A 39. B 40. B 41. A 42. B
43. A 44. B 45. A 46. C 47. B 48. B 49. B
50. A 51. A 52. A
Exercise - 2 (Level-I) Objective Problems | JEE Main
1. C 2. A 3. B 4. A 5. A 6. B 7. A
8. B 9. A 10. C 11. B 12. B 13. A 14. D
15. D 16. A 17. D 18. B
Exercise - 2 (Level-II) Multiple Correct | JEE Advanced
1. A 2. D 3. A 4. A 5. (B, D) 6. (A,B) 7. B, C
8. D 9. D 10. A
11. A S ; B R ; C Q ; D P 12. A T ; B S ; C R ; D Q; E P
13. A P, Y ; B Q, X ; C R, W 14. A S ; B R ; C Q ; D P
15. A R ; B Q ; C P ; 16. A P ; B Q ; C R ; D S; E T
17. A S ; B Q ; C R ; D P
Exercise - 3 | Subjective | JEE Advanced
1. A 2. B 3. B 4. C 5. A 6. A 7. A
8. C 9. C 10. B 11. A 12. A 13. B 14. A
15. A 16. A 17. C 18. B 19. B 20. C 21. C
22. A 23. A 24. D 25. C 26. C 27. D 28. B

29. A 30. C 31. A 32. D 33. A 34. C 35. D
36. B 37. A 38. C 39. A 40. A 41. A 42. B
43. C
Alkyl Halide
Exercise - 4 | Level-I Previous Year | JEE Main
1. A 2. C 3. D 4. A 5. C 6. B 7. C
8. D 9. A 10. D 11. B 12. B 13. B
14. A
SbCl5
CH – CH3 CH – CH3
Lewis acid
Carbocation
Cl
15. D
SN2
1
Reactivity of SN2 
Steric hindrance
Order of reactivity towards SN2.
CH3Cl > CH3–CH2–Cl > (CH3)2CH–Cl > (CH3)3C–Cl
16. D
R–Cl
AgF/dmF
or R–F + AgCl/AgBr
R – Br
Swart reaction
17. A
Due to presence of bulky base product would be an alkene.
18. A
Intermediate  Carbocation
CH2
CH3–CH–CH2–CH3 CH3–CH2–CH2
OCH3
+M
(III) > (I) > (II)
19. D
O
Br
Unable to form alkene
So decolourisation
Can't be possible.
Alkyl Halide
20. A 21. C 22. D 23. A 24. A 25. D 26. A

27. A 28. D 29. D 30. B 31. B 32. A 33. B
34. D 35. C 36. B 37. D 38. A
39. C
Cl Cl Cl Cl
NO2 O2 N NO2
(–M &–I)
NO2 NO2 NO2

(– M & –I) (– M & –I) (– M & –I)
(i) (ii) (iii) (iv)
Reactivity  – M group present at o/p position.
40. C
Only 1º amines can be prepared by Gabriel synthesis.
41. D
OCH3 OCH 3 OCH 3
+ – Cl I
H Cl NaI
dry acetone
NO2 NO2 NO2

(A) (B)
42. C
Cl
N 2+Cl–
Cu2Cl2
(a) + N2
(Sandmeyer reaction)
Cl
N 2+Cl–
Cu,HCl
(b) + N2
(Gatterman reaction)
Ether
(c) 2CH 3–CH 2Cl + 2Na C2 H5 – C2 H 5+2NaCl
(Wurtz reaction)
Ether
(D) 2C6H 5Cl + 2Na C6H 5 –C6H 5+2NaCl
(Fitting reaction)
Alkyl Halide
43. B
OH OH
SOCl 2
HO CH2 OH Cl CH 2 Cl
44. D
Br
CH 2–CH 3
CH
CH 3
2Br /UV light
  

CN
CN
It is bezylic substitution reaction
45. C
CH3
Br
NaNH2 red hot Fe-tube
CH3 – CH = CH CH3 – CH CH
CH 3 CH3
(mesitylene)
46. B
C2H5OH & AgCN both can generate nucleophile
AgCN & KCN both not generate nitrite nucleophile in all reaction condition.
47. A
CH3 OH CH3
20%/H3Po4
358 K
Saytzeff's alkene(A)
CH3 Cl CH 2
– +
(CH3 )3CO K +
Hoff mann's alkene(B)
Alkyl Halide
48. D
Cl Cl
Cl 2 Cl 2
h h
Cl
49. D
NH 3 R– X R2NH
R–X R-NH2
–HX –HX
–HX R–X
R–X R3 N
R4NX
During the reaction HX (acid) is form

Hence, we use NaOH to remove this acidic impurities
50. A
Based on NCERT
51. C
Based on NCERT
C6H5CH2Cl + NH3  C6H5CH2NH2
52. A
e
e
O O
C N
O O
O –N = O O
O
More than one e donating side

 
53. D
a/c. KOH  Used for B. elimination reaction
Pd/ Ba son  Lindlar’s catalyst
BHC (Benzon lexa chloride)  Addition product of benzen and chloride.
Poly actylene  Used in electrods in batteries
Alkyl Halide
Exercise - 4 | Level-II Previous Year | JEE Advanced
1. A 2. A 3. D
O
4. (x) (y)
CH3–C–(CH2)4–CHO
CH3
5. AQ ; BQ ; CR,S, ; DR,S,
6. B 7. A 8. A 9. D 10. D 11. D 12. C

13. A 14. 5 15. B 16. B 17. ABC 18. 5 19. A, D
20. B 21. B 22. A,B 23. A
Alkyl Halide
ALKYL HALIDE

1. D
H – I > H – Br > HCl
2. D
Re d P Br
(A) C2H5OH   C2H5Br
SOCl2
(B) C2H5OH   C2H5Cl + SO2 + HCl
KBr  conc. H2SO4
(C) C2H5OH   C2H5Br + KOH
3. C
Pyridine
ROH + SOCl2 R–Cl + SO2 + HCl
4. A
COOAg Br
Br2
acetone
Hunsdiecker reaction
5. B
The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because the other
products of the reaction are gaseous and escape out.
C2H5 OH + Cl–SO–Cl  C2H5 Cl + SO2+ HCl
ethanol ethylchloride
It is one of the most important methods for preparing alkyl halides.
6. C
ROH + SOCl2  RCl + SO2 + HCl. It is evident that products other than RCl, are both gases
(SO2, HCl)
7. C
In Hunsdiecker reaction a silver salt of an acid reacts with bromine in the presence of CCl4.
CH3COOAg + Br2 CCl 4  CH3Br + CO2 + AgBr
silver ethanoate bromomethane
It is an important method of preparing an alkyl halide from a silver salt of an alkanoic acid.
8. B
Acetone
CH3CH2Br + NaI CH3CH2I + NaBr
9. C
CH3COOAg + Br2 CCl 4 CH3Br + AgBr + CO2
10. D
NaI + CH3COCH3
11. B
C2H5Cl + AgF 
 C2H5F + AgCl
Swart reaction
12. D
CH2–Cl + NaOH CH2–OH + NaCl
13. B
SN2 reactivity order
sizereactivity
Order of leaving group I > Br > Cl > F
Alkyl Halide
14. C
SN1 reaction in first step carbocation from carbocation
–
X X Nu Nu
15. B
As Rate k = [RCl], on decreasing the concentration of RCl to half the rate will also be halved. Rate
will also increase with temperature.
16. D
Since electrons are in resonance with ring.
17. D
H2C=CH–Cl lone pair will be in resonance with ring hence C–Cl bond have double bond characters.
18. A
R – Cl + Na+O– – C2H5  R – OC2H5 + NaCl
19. A
H H
1
SN C2H5ONa
CH3 – C – C – CH3
CH3 Br
H H H H
–
1.Step CH3 – C – C – CH3 CH3 – C – C – CH3 + Br
CH3 Br CH3
–
1,2 H
CH3 – C – CH2 – CH3
shift
CH3
H H
–
O C2H5 CH3 – C – C – CH3
OC2H5 CH3
CH3 – C – CH2–CH3 OC2H5
CH3
H H
CH3 – C – C – CH3
CH3 OC2H5
20. B
Cl2 Alc.KoH
CH3 – CH3   CH3 – CH2 Cl   CH3 – CH2 – OH CH3 – CHO
21. B
R – X + KCN  R – CN + KX
22. B
alc.KOH
CH3— CH2—Cl 
 CH2=CH2
Elimination reaction
23. B
C2H5–Br + Ag2O  C2H5–OH + AgBr
moist
Alkyl Halide
24. A
2C2H5-OH + 2Na  2C2H5ONa + H2
(A) (B)
C2H5–OH + PCl5  C2H5-Cl + POCl3 + HCl
(A) (C)
C2H5–ONa + C2H5–Cl  C2H5–O–C2H5 + NaCl
(B) (C) diethyl ether
25. B
Both vinyl chloride and chlorobenzene give no precipitate with alcoholic AgNO3 because both have
chlorine atoms which are not reactive.
26. C
The number of step involved in SN1 and SN2 mechanisms are given by the set 2, 1
The SN1 reaction takes place in 2 steps as follows
CH 3 CH 3 CH3
Fast
CH3 C–Br Slow CH3 C+ OH –
 CH3 C–OH
First step Br  Second step
CH3 CH3 CH 3
t- butyl bromide carboniumion t-butanol
The SNII reaction takes place in 1 step as follows -
–
 OH
CH3–Br  [HO——CH3——Br]
Slow
methyl bomide (one step transition state)

–
 CH3OH + Br
Fast

methanol
27. B
Tertiary butyl halide on boiling with water gives tertiary butyl alcohol. The reaction following SNI
mechanism.
CH 3 CH3 CH3
CH3 C–Cl  CH3    OH 
C –Cl  CH3
Slow
C–OH
Fast
CH3 CH 3 CH 3
t-butyl alcohol
t-butyl chloride
The slow step is the formation of a carbonium ion, hence the reaction takes place via SNI mechanism.
28. A
Inversion of configuration of the product alcohol during the hydrolysis of an optically active halide
is an experimental evidence for SN2 mechanism. The reaction takes place as follows :
CH3–Cl + OH– (chloromethane) 
[HO——— CH3 —— Cl]  HO–CH3 + Cl¯
transition state methanol
Here OH– attacks from the back side on CH3 Cl molecule, hence the product formed has an inverted
configuration.
29. B
CH3–CH=CH–CH3 + HI
CH COOH
 CH3–CH2–CH–CH3
3 
I
(electrophilic addition reaction)
CH3–CH2–CH–CH3 + NaOH (aq.)
I
 CH3–CH2–CH–CH3
OH
(nucleophilic substitution reaction)
Alkyl Halide
30. C
An alkyl isocyanide is prepared by the action of AgCN on alkyl halide
CH3 Cl + AgCN  CH3 N  C + AgCl
methanisonitrile
Isonitrile on reduction produces secondary amine.
31. A
CH3–Br + AgCN ––– CH3–N  C (A) H2O CH3NH2 (B) + HCOOH

32. A
Reaction of ethyl bromide and silver acetate gives ethyl ethanoate It is an ester formation and has
got a fruity smell.
CH3COOAg + BrC2H5  CH3COOC2H5 + AgBr 
silver acetate ethyl ethanoate
33. C
H H
H–CC–H HBr HBr
H – C = C – Br
H H
H – C – C – Br (Product)
H Br
34. A
Cl
H2O
CH3 – C – CH3
Cl
OH O
CH 3 – C – CH3 CH3 – C – CH 3
–H2O
OH
35. D
Cl Cl
CH3–CH2—CH + 2Zn + CH – CH2 – CH3
Cl Cl
CH 3–CH 2–CH=CH–CH 2–CH 3+2ZnCl 2
36. B
Phosgene (COCl2) gas.
37. D
Chloroform can be prepared from 2º alcohol or by ketone.
38. A
I2 Ag
CH 3–C–CH3 CHI3 CH CH
Na2CO3 Powder
O
HgSO4
O
CH3 – C – H
39. B
O
type compounds gives idoform test.
Alkyl Halide
40. B
1 % Alcohol (C2H5OH)
41. A
: CCl2
42. B
ph– NH2 + CHCl3 KOH ph – N  C
43. A
Those compounds that can react with I2 + NaOH will give a yellow ppt and gives idoform test.
O
methyl ketone type groups gives idoform test. The yellow ppt will of CHI3.
44. B
Carbon tetrachloride (CCl4) has tetrahedral structure and its 4 polar C–Cl bond cancels each others
dipole moment which results in net dipole moment zero.
45. A
Due to - I effect, Cl atoms tend to attract the electrons of C–H bond towards themselves.
46. C
On heating C–I bond breaks, but C–Cl bond does not break. Thus, AgNO3 gives Agl with iodoform.
47. B
Pyrene is the commerical name of a fire extinguisher CCl4. It is the only organic cmpound which is
non inflammable and which is used to extinguish fire.
48. B
R–COOAg + Br2 CCl 4  R–Br + CO2 + AgBr 
The yield of alkyl bromide has the following order
R
R–CH2–Br > R–CH–Br > R–C–Br
R R
Since the mechanism of this reaction involves formation of free radicals.
49. B
When alkyl halides are exposed to sunlight they becomes darken.
50. A
Density of a given alkyl group increases with increase in atomic weight of halogen atom. but for a
given halogen density decreases with increase in size of alkyl group.
51. A
With alcoholic AgNO3, ethyl bromide gives a light yellow and isopropyl chloride gives white ppt.
52. A
CH2–CH2+2KOH – CH2– CH2+2KCl
Cl Cl (aq.) OH OH
1,2-dichloroethane ethane–1,2-diol
CH 3–CH–Cl+2KOH
Cl (aq.) – CH3–C–H
 CH3–CH–OH
 H O
2
1,1-dichloroethane OH O
Alkyl Halide
Exercise - 2 Level - 1 | JEE Main

1. C
(a)
order of rate  r2 > r1 due to better leaving group than
(b) CH3–CH2–CH2–CH2–Br NaI

r1
Acetone
order of rate  r1  r2
2. A
3. B
+
H /HO
2 + +
R – OH R – OH2 R (Carbocation)
.. +
–H +
R – OH R – OH2
Corbocation as intermidiate
4. A
Br
CH3 H CH3 H
CH3 H
C===C
–Br2
H CH3
H CH3 H CH3
Br (Major)
5. A
(A)
Alkyl Halide
(B)
(C)
(D)
6. B
7. A
(A) (B) (C) (D)
most reactive for SN1 or SN2

[leaving tendency of leaving  rate of SN1 or SN2 group]
in above option leaving tendency of leaving group. 
So, (A) Most reactive for SN1 or SN2
8. B
CH3
Cl
This compound gives four SN1 product.
9. A
[Mechanism of SN2 reaction]
Alkyl Halide
CH2 — H CH 2
| ||
CH3 — C — Br + CH3 — O CH3 — C + CH3OH + KBr
| |
CH2 CH3
S.B. elimination
3º alkyl halide
3º alkyl halide react with sodium methoxide and gives alkene not ether because reaction will be
elimination not substitution
CH3
SN2
CH3 — Br + NaO CH 3
CH3
CH3
|
CH3 — O — C — CH3 + NaBr
|
CH3
11. B
Zn + ZnBr2
 
Both Br are eliminate from adjacent corbon that is called  elimination.
12. B
H(2)
Br
E2(OH )
+
H (1)
(1) (2)
(Major)
(More Stable)
13. A
Following comp. cannot undergoes an E2 reaction.
CH3 CH2–Br
So, not give E2 reaction.

14. D
Br
(A) (CH3)3C–O K +
bulky Nu Major
(CH3)3C–O K
(B) bulky Nu
4-Methyl-2-hexen
Br
Alkyl Halide
(CH3)3C–O K 5 3 1
(C) 3-Methyl-2-hexen
bulky Nu 6 4 2
Br
(CH3)3C–O K
(D) bulky Nu 3-Methyl-1-hexen
Br
Less steric hindred proton will be eliminate so hoffmann product will be formed.
15. D
H
CH3
E2
No. Reaction
Anti elimination
Br
H
CH3
Both H are same side of Br. So, H or Br are not eliminate. Reaction are not possible.
16. A
CH3
(OH ) CH3
Antielimination 3-Methyl cyclohexene
Cl
H
This H will be eliminate
17. D
CH3–CH2–CH–CH3 CH3–CH2–CH=CH2
| 1-butene
NMe3
(Hofmann product)
bad leaving
Group
18. B
H
CH3 CH3
Alcoholic KOH
–HBr
Br
CH3
CH3
Alkyl Halide
Exercise - 2 Level - 2 | JEE Advanced

1. A
Rate of SN1  stability of carbocation Reactivity order of Alkyl halide towards SN1 reaction
CH3
CH3 C Cl > CH3 CH Cl > CH3 CH2 Cl > CH3 Cl
CH3 CH3
3o 2o 1o
alkyl halide alkyl halide alkyl halide
2. D
Steric
[ rate of SN2  ( less hindered T.S ) ]
reactivity order of Alkyl halide towards SN2 reaction
CH3
CH3 Cl > CH3 CH2 Cl > CH3 CH Cl > CH3 C Cl
CH 3 CH3
o
1 2o 3
o
halide halide halide
3. A
Most reactive towards E2 is t-bulyl chloride
t - bulyl chloride
Base
H - CH2 6H
Cl
It gives more stable alkene

4. A
Most reactive towards E1 is also t - butyl chloride because it gives most stable carbocation
Cl
Cl—
9H
5. B,D
This SN2 reaction.
6. A,B
CH3
CH3 Moist Ag2O CH3

Ring expansion
CH2–Cl SN1
AgOH
CH3 OH
Alkyl Halide
7. B,C
SN1 Product
–Cl 1–2H OH OH
Shift
Cl
(A)
SN2 product :
A, B are different.
Cl
H S N1 OH
(B) H
SN2
OH
H (S N1 or S N2 product are same)
OH
(C)
8. D (High temperature, Distillation)

9. D
Total number of  - hydrogen A + B + C = 29
(i)
(ii)
OH OH2
(iii)
Alkyl Halide
10. A
OH
(A) (B)
OH
OH
(C) (D)
11. A–S, B–R, C–Q, D–P

Rate of SN2  less steric hindered T. S. order of reactivity of primary alkyl bromide for SN2
CH3 – CH2 – Br > CH3– CH2 – CH2 – Br >
Me
Me—CH—CH—Br2 >Me—C—CH—Br2
Me Me
12. (A)  T (B)  S (C)  R (D)  Q (E)  P

Presence of water, ethanol (weak Nu). Rx will be procced According to S.N. Mach.
13. A–PY, B–QX, C–RW

Reactivity order of alkyl halide for E2 elimination
 3° alkyl halide > 2° alkyl halide >1° alkyl halide reactivity order of alkyl halide for SN2 RxN
 1° alkyl halide > 2° alkyl halide > 3°alkyl halide
14. (A S B R C Q D P)
Leaving group are different in all substrate
So
15. (A R B Q C P)
reactivity order of alkyl halide for SN1 mech
CH 2
CH3 - C - Br > CH3 - CH - Br > CH3 - CH2 - Br
CH 3 CH 3
3 alkyl halide > 2o alkyl halide > 1o alkyl halide

o
16. (A)  P (B)  Q (C)  R (D)  S (E)  T

Rate of SN1 is not depend Nu - so water is weak Nu - than ethanol. So Rxn will be proceed SN1
Mech in Presence of water solvent but in presence of ethanol solvent Rxn will proceed SN2 Mech
17. A S B Q C R D P
CH3 O
Z - CH2 - Br Z - CH2 - OCH 3- Br
SN2
here Z group will be Small than rate of SN2 will be increaced.
Alkyl Halide
Exercise - 3 Subjective| JEE Main

1. R – OH + NaBr  R – Br + NaOH
This reaction is not possible because is bad leaving group. So not leave easily from .
Ans. A
O–CH3 OH
 CH3
O

H / H2O | 
H + CH3
2. (A) H2 O
CH3–OH
(B)
C – O bond is not breaked due to double bond character. So this comp is not hydrolysed.
(C)
(D)
Ans. B
3. Order of SN2 reactivity of following comp.
bredt's
order of SN2 reactivity III > II > I

Ans. B
4. (A) (B)
(C) (D)
Ans. C
Alkyl Halide
5. SN2 reaction proceed in presence of strong nucleophile.
Nucleophilicity  steric and hindrance reactivity order of nucleophile towards SN2
Ans. A
6. A
Internal
Nu Ph
external Nu
SPh H S Phs H
2
SN
H Cl (intra molecular H H Nu
2
SN )
H H
Internal and leaving group are present at same side so SN NGP are not possible.
sph Cl
Ans. A
7.
OCH3 2 OH
(X) con. HI
+ 2 CH3 – I
OCH3 OH
H
|
O — CH3 O CH3 OH
(1) HI I
+ CH3I
O — CH3 OCH3 OCH3
(2) H I
OH OH
CH3I +
OH O — CH3
|
H
Ans. A
8.
OCH3 I
(X) con. HI
+ 2 CH3 — I
=5
OCH3
OCH3 OH
2 HI
+ 2 CH3 — I
OCH3 OH
–2H2O 2HI
I
due to
large size of
– I2
I (I)
Ans. C
Alkyl Halide
9.
con.
I I
+
H
Ans. C
CH3 CH3 CH3 CH3
| | | |
10. Ph — CH — C — CH3
EtOH
Ph — C — C — CH3
| (SN1) | |
Br Oct H
CH3 CH3 CH3 CH3

| | Slow step
| |
Mechanism Ph — C — C — CH3 Ph — C — C — CH3
| | (SN1) |
H Br H
1-2 H
shift
CH3 CH3 CH3 CH3 CH3 CH3

| | –H | | EtOH | |
Ph — C — C — CH3 Ph — C — C — CH3 Ph — C — C — CH3
| | | | |
OEt H O H H
Et H
Ans. B
11. CH3 CH3
SOCl2
S S
H OH H Cl
SNi
Et Et
Retention configuration will be
occur in this mechanism
CH3 CH3
Cl Cl
HCl(g)
H OH S == O H O S O
|
Cl H Cl
Et Et
CH3 CH3 CH3
O O
H Cl H S=O H S=O
Et Et Cl
Et Cl
4 M C.T.S
Ans. A
Alkyl Halide
12. A
E
+
H +
13. B
excess
O O
HO O H OH
14. A
in above reaction [Cl (I)] are easily remove from reactant because formed corbocation will be more
stable due to back bonding.
15. A
reactivity order for SN1 reaction  (III > I > II)
Alkyl Halide
reactivity order for SN1 reaction  stability of corbocation.
16. A
CH2OH CH2Br
HBr
OH OH
Not break due to D.B.C.
17. C
CH3 CH3
(i) SH S
CH3 — CH — CH2 — CH2 — CH — CH3
| | (ii) KOH
OTs OTs
Mech.
SH
18. B
19. B
OAc
t-Bu +
OTs AcO Na
t-Bu
Alkyl Halide
20. C
Br _ Br
+
(1) NaNH2
Ph CH CH2 Ph CH = CH
NH3 _
+
Br Nabr (1) NaNH2
NH3
_
Ph C = CH
PhC C H NaBr Br
No of moles of NaNH2 ( ) = 2
21. C
H
CH3 CH CH3 CH3 CH CH3
OH OH2 - H2O
a b
CH3 CH CH3
c
carbocation H
intermediate
c CH2 = CH CH3
d
d
a
b
22. A
CH3 CH 3
+
H
CH3
OH CH3
CH3 CH3 CH3

H
CH CH3 CH3
.. 3
OH OH2 +
1-2 CH3
Shift
CH3 CH3
CH 3 H CH3
23. A
OH
H OH2
1-2 CH3
(A) Shift
Alkyl Halide
H
(B)
OH OH 2 1-2 H Shift
(C) OH H
OH 2
1-2 H Shift
OH 2
H
(D)
OH
no Rearrangement
24. D
25. C
CH2 OH CH2
con. H 2SO4 Allylic
(P)
r1 1 carbocation
OH
CH3 CH3
con. H 2SO4 Allylic
(Q)
r2 2 carbocation
OH
CH3 CH3
con. H 2SO4
(R)
r3 3 carbocation
Allylic
OH
CH3 CH3
con. H 2SO4
(S)
r4 3 carbocation
Allylic
(rate of dehydration  stability of carbocation )

order of rate of dehydration  r3 > r2 > r1 > r4
R>Q>P>S
Alkyl Halide
26.
Con. H2SO 4
HO OH
HO OH
OH2
OH
OH2
HO OH
HSO4
2 Tautomerism
H2O HO HO OH
Ans. C
27. D
Me Me
Con. H2 SO4
Me
OH HO Me O
( Pinacole ) ( Pinacolone )
This is pinacole - Pinacolone Rearranagement

Me Me
H
Me Me
OH OH OH OH2
Me
Me
OH
Me Me
-H
Me
Me
OH
28. B
Me Me Et
H Et alc KOH
Br Et
Et Me
Me Me
Me Et Br
Me Me
H Et o
= 180
Br Et
H Et Et
Br Et H Me
Me
Anti elimination
Me
Me Et
Me Et
Et
C C Et
Et Me Et Me
Trans Me
Erythro + Anti Trans
Alkyl Halide
29. A
OEt OEt
H  
 OEt

(A) H / H2O
O Et   – etOH
OEt

H / H 2O
OEt  OEt   
(B)  – etOH
H
Et
H / H2O O–H  
 Et + etOH
(C)   – etOH
Et
 
H / H O
(D) EtOH  2 Et OH2   E t
– H2 O
CH3  CH2
(reactivity of acidic hydrolysis  stability of carbocation of alcohal)
(A) is most stable corbocation due to back bonding.
30. C
Br H(2)
| |
| C—CH—CH3
H |
(1) CH—CH2—CH3
|
H(3) G.I.
C—CH2—CH3
||
CH—CH2 —CH3
C—CH2—CH3 (2)
|
CH2—CH2—CH3 G.I.
(1) C==
= CH—CH3
not G.I.
|
CH2—CH2—CH3
(2)
Total no. of product (1 + 2 + 2) 5
31. A
bulky Nu
CH3 CH3 CH3

|
H3C–C–OK CH2
Br | CH3
CH3 CH3 +
E2
CH3
(Major)
(Hoffmann Product)
in presence of highly branched base hoffmann eliminated product will formed.
32. D
()
()
Alkyl Halide
()
[]
33. A
•• ••
CH3OH CH3OH ••
CH3–O–CH=CH2 CH3–O–CH–CH3 CH3–O–CH–CH3
H |
H–O
CH3
CH3 O
CH–CH3
CH3 O
(Acetal)
34. C
(1)
(2)
Br
|
CH3–CH2–CH2 –C–CH2–CH3
|
CH3
E1
Show G.I.
CH3–CH2–CH=C–CH2 –CH3 CH3–CH2–CH2–C–CH2–CH3

| Show G.I. ||
CH3 CH2
(1)
(2)
CH3–CH2–CH2–C=CH–CH3
|
(2) CH3
Total no. of products = 7.
35. D
Alkyl Halide
–H2O 1–2 CH 3shift
OH OH2
–H
(B)
••
OH OH2
–H2O
Resonance stable
(C)
(Stability order of following product)

[C > A > B]
36. B
(A) (B) (C)
(B) are less reactive in () dehydrohalogenation because H and Cl are present towards same
side so not elimination.
37. A
The nitrogen atom that is not bounded to any ring will be mosty easily removed as trimethyl amine.
38. C
–
OH
OH–
Mechanism
OH–
39. A
Alkyl Halide
40. A
CH3 CH3
CH3 CH2 CH CH3 alc KOH C =C

Br H H
CNS -2-butene
CH3 + N
C =C
N CH3
Trans -2-butene
(Major)
+
CH2= CH CH2 CH3
1-butene
H
(i) OH
H2O
(ii) H
OH
H2O
H
(iii) OH
H2O
H
(iv) OH
H2O
rate of delydration stability of carbocation stability order of carbocation

( iv > iii > ii > i ) rate of dehydration order ( iv > iii > ii > i )
Ans. A
42. B
CH3 CH3
CH3 CH2 CH CH3 alc KOH C =C

Br H H
CNS -2-butene
CH3 + N
C =C
N CH3
Trans -2-butene
(Major)
+
CH2= CH CH2 CH3
1-butene
Alkyl Halide
Ph Ph Ph Ph
C C C C
con. H 2SO4
OH OH OH2 OH
MeO CH3 MeO CH3
H2O
Ph Ph
C C
OH
MeO CH3
Ph
Ph C C MeO MeO C C
H
OH
CH3 CH3
43. C
In E2 elimination reaction.
rate of reaction  (alkyl halide ) (base )
Alkyl halide and base both are participate in slowest step so rate of reaction is depend on both
conc. of alkyl halide and base.
Alkyl Halide
Exercise - 4 | Level-I Previous Year| JEE Main

1. A
Order of thermal stability of Hx  HF > HCl > HBr > HI
2. C
Tertiary alkyl halide having more steric hindrence. so less reactive tor SN2 Mech.
3. D
R’ – X + R2Cu  R’ – R + RCux
4. A
H
alc. KOH + +
Br (major)
5. C
Compound having CH3 – C – , CH3 – CH – , group show. Idoform. Test
O OH
6. B
Reactivity order of alkyl halide towards SN2
R–CH2– X > R2CH–X > R3C–X
7. C
CH3–Cl show SN2 reaction and gives inversion product.
8. D
Cl aq. KOH OH
CH3–CH CH3–CH
Cl OH
-H2O
  CH3CH=O
9. A
Reactivity order of alkyl bromide towards SN1.
> > Br
Br Br
10. D
CH3 CH3
CH3 C CH3 CH3 C CH2 X
CH3 CH3
(Only monosubalkyl halide)

[Molecular mass of neopentan = 72 U ]
11. B
CH 3 – CH – CH 2 – OH
CH 3
(Isobutyl alcohol) donot give iodoform test.
12. B
DDT. is a non biodegradable pollutant.
Alkyl Halide
13. B
CH 2Br CH2
AgNO3 + AgBr
CH3 CH3 O
(A) COOH
[O] C
– H2 O O
COOH C
(B) (C)
O
Pthalic anhydride
14. A
CH – CH3
SbCl5
SbCl6
CH – CH3 
- *
Lewis acid CH—CH3
Carbocation
Cl Cl
(Recemic mix.)
15. D
SN2
1
Reactivity of SN2 
Steric hindrance
Order of reactivity towards SN2.
CH3Cl > CH3–CH2–Cl > (CH3)2CH–Cl > (CH3)3C–Cl
16. D
R–Cl
AgF/dmF
or R–F + AgCl/AgBr
R – Br
Swart reaction
17. A
Due to presence of bulky base product would be an alkene.
18. A
Intermediate  Carbocation
CH2
CH3–CH–CH2–CH3 CH3–CH2–CH2
OCH3
+M
(III) > (I) > (II)
19. D
O
Br
Unable to form alkene
So decolourisation
Can't be possible.
O HI I
20. A heat
O OH
Alkyl Halide
21. C 22. D 23. A 24. A 25. D 26. A 27. A
28. D 29. D 30. B 31. B 32. A 33. B 34. D
35. C 36. B 37. D 38. A
39. C
Cl Cl Cl Cl
NO2 O2 N NO2
(–M &–I)
NO2 NO2 NO2

(– M & –I) (– M & –I) (– M & –I)
(i) (ii) (iii) (iv)

Reactivity  – M group present at o/p position.
40. C
Only 1º amines can be prepared by Gabriel synthesis.
41. D
OCH3 OCH 3 OCH 3

Cl I
H +Cl– NaI
dry acetone
NO2 NO2 NO2
(A) (B)
42. C
Cl
N 2+Cl–
Cu2Cl2
(a) + N2
(Sandmeyer reaction)
Cl
N 2+Cl–
Cu,HCl
(b) + N2
(Gatterman reaction)
Ether
(c) 2CH 3–CH 2Cl + 2Na C2 H5 – C2 H 5+2NaCl
(Wurtz reaction)
Ether
(D) 2C6H 5Cl + 2Na C6H 5 –C6H 5+2NaCl
(Fitting reaction)
Alkyl Halide
43. B
OH OH
SOCl 2
HO CH2 OH Cl CH 2 Cl
44. D
Br
CH 2–CH 3
CH
CH 3
2Br /UV light
  

CN
CN
It is bezylic substitution reaction
45. C
CH3
Br
NaNH2 red hot Fe-tube
CH3 – CH = CH CH3 – CH CH
CH 3 CH3
46. B (mesitylene)
C2H5OH & AgCN both can generate nucleophile
AgCN & KCN both not generate nitrite nucleophile in all reaction condition.
47. A
CH3 OH CH3
20%/H3Po4
358 K
Saytzeff's alkene(A)
CH3 Cl CH 2
– +
(CH3 )3CO K +
Hoff mann's alkene(B)
Alkyl Halide
48. D
Cl Cl
Cl 2 Cl 2
h h
Cl
49. D
NH 3 R– X
R–X R-NH2 R2NH
–HX –HX
–HX R–X
R–X
R4NX R3 N
During the reaction HX (acid) is form

Hence, we use NaOH to remove this acidic impurities
50. A
Based on NCERT
51. C
Based on NCERT
C6H5CH2Cl + NH3  C6H5CH2NH2
52. A
e
e
O O
C N
O O
O –N = O O
O
More than one e donating side

 
53. D
a/c. KOH  Used for B. elimination reaction
Pd/ Ba son  Lindlar’s catalyst
BHC (Benzon lexa chloride)  Addition product of benzen and chloride.
Poly actylene  Used in electrods in batteries
Alkyl Halide
Exercise - 4 |Level-II Previous Year| JEE Main + Adv.

1. A
CH 3 CH3 CH 3
NO 2
(K)
H Cl CH 3
CH 3 CH3 CH 3
NO 2 (L)
H OH CH 3
Product K formed through simple nucleophic subsititution SN1 while product L is formed through
hydride shift (H–) through SN1 and CH3O– (methoxy) group stebilizes the carbocation of product (L).
2. A
OH conc.H Po
3 4
dehydrating
agent
3. D
Cl
two equivalent
of Na/ether
Br
1-bromo-3-chloro
cyclo butane
OH
H+, ring
4.
expantion
CH 3
O
(1) O3
(2) Zn/Cu3COOH CH3 – C –(CH2)4 – CHO
O
(x) (y) CH3–C–(CH2)4–CHO
CH3
5. [A – Q; B – Q; C – R, S; D – R,S ]
alc koH
(A) CH3– CH – CD3   CH2 = CH–CD3
| E2e lim ination
Br
alc koH
(B) Ph– CH  CH3   r1 r1  r2
|
Br
Alkyl Halide
alc koH
(C) Ph– CH –CD3   r2
|
Br
C2H50D / C 
2H5O
(D) Ph–CH2–CH2–Br     
E1cbe lim ination
Ph–CH=CH2
(E) rate of reaction PhCH2–CH2Br >
Ph–CD2–CH2–Br
Due to isotopic effect
6. B
Br
Br
Br alcoholic 
Br CH=CH
KOH –Br 
H Br H
 
NaNH2
CH  CH
NaNH2  alcoholic kOH 

Strong Base 
aqueous kOH
7. A
CH 3 H
C=C +Br2  Meso comp.
H CH 3
8. A
Me R Br Me SPh
S
F F


Ph S Na
  

diethyl
formamide
NO2 NO2
Reaction proceed Via SN2 mech.
9. D

(I) O
3º carbocation/backbonding

(II)
2º secondary/carbocation

(III) O
2º carbocation by stable by back bonding
(IV)

Primary carbocation
stability order  I > III > II > IV
Alkyl Halide
H H
1 2  1-2 Hshift
10. D HC C C C CH3
3
OH H CH3
 2
CH3–C–CH2–CH–CH3
OH CH3
(Carbocation will be stable by back bonding)
11. D
 
CH3–CH2–CH2–CH2 Br + CH3 – CH 2 – C C Na
CH3–CH2–C CH
+NaNH2
8 7 6 5 4 3 2 1
CH3–CH2–CH2–CH2–C C–CH2–CH3
3-Octyne
NaNH2
CH3–CH2–C  C–H  
Br
CH3–CH2–CC–CH2–CH2–CH2–CH3
12. C
(C–C) bond energy  100 kcal/mole.
13. A
O O
C
(i) KOH 
NH N
H2O CH2–Cl
C
O
O
Br
O
N–CH2 Br
14. 5
Br
2
CH3–CH2– C –CH2–CH2–CH3 alcoholic kOH
  CH3– CH=C–CH2–CH2–CH 3
CH3–CH2– CH=CH–CH2–CH 3 CH3–CH2– C–CH2–CH2–CH 3
2
1
15. B
RCH2OH
+
H (anhydrous)
O O OCH2 – R
Acetal
Alkyl Halide
16. B
S>P>R>Q
O
=
Transition state of compound S is highly stabilize by Ph – C – group so it has more rate of reaction
towards SN2.
order of stability of T.S. S > P > R > Q.
In compund R, T.S is stabilize by p-orbital attached to carbon having leaving group.
17. ABC
OH OH
OH
Br Cl Cl
I
Products and
C(CH3)3 C(CH3)3
C(CH3)3
Br Cl
are explained by steric effect of halogen & t-butyl group and electronic effect of phenolic group.
18. 5
CH 2CH2CH3
Br2(1.0 mole)
H Br
CH 3
(1.0 mole)
(enantiomerically pure)
CH3
CH2 – Br
CH3 CH3 CH2
(1) (2) (3) CH2
CH2 (4) CH3
CH2 CH2 (5)
H Br CH2 Br H
Br H H Br
H Br H
H Br
H Br Br
CH3 CH3 CH2 – Br CH3
CH3
19. A, D
Br
I is (1° benzylic halide) and
C
C – C – Br (3° alkylhalide) fellow SN1
C
(B) I and II follow SN2 also as both are 1° halide
(C) Compound (iv) undergoes inversion of configuration due to presence of chrial carbon atom
20. B
Me N3
(1) PBr3Et2O
X
(2) NaI, Me2C = O
(3) NaN3, HCONMe2
Me OH
all the three reaction are SN2 so X is
Alkyl Halide
21. B
H3C H3C H3C CH2

CH3 CH3 CH 3
E2
+ +
P:
H3C H3C H3C H3C CH 3
ONa Br OH
(i) (iv)
CH3
H3C
CH3
Q : H3C O + HBr + MeOH
CH 3 H3C
Br
CH3
H3C CH2
CH3
— +
R: MeO Na
E2
H3C H3C CH 3
Br
H3C H3C
CH3 2
CH 3
SN
S: + MeBr
H3C H3C
ONa OMe
22. A, B
O Cl
HO CH3 CH3
(i) MeMgBr Conc. HCl
(ii) H2O
C 6H 10O (Q) (S) (major)
20% H3PO3, 360K
CH 3 Br
CH3 Br
CH3
(i) H2, Ni HBR, benzoyl peroxide
(ii) Br2, h
T R
(major) (major)
23. A

Alkyl Halide 1631899631060

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Alkyl Halide 1631899631060

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CONTENT

1.1 ALIPHATIC HALOGEN DERIVATIVES :

Alkyl halides : Monohalogen derivatives of alkanes are known as alkyl halides

Structure of alkyl halides:

Classification of alkyl halides :

Halolkanes can be classified into following three categories.

5. CH 3 – CH – CH 2 – CH2 – CH2 5-chloropentan-2-ol

1.3 ISOMERISM IN HALOALKANES

S.N. Compound IUPAC name

(a) Chain 1. CH3 – CH2 – CH2 – CH 2 – Cl 1-Chlorobutane

2. CH3 – CH2 – CH 2 – CH 2 – CH2 – Cl 1-Chloropentane

(b) Position 1. CH3 – CH 2 – CH2 – Cl 1-Chloropropane

2. CH3 – CH – CH2– Cl 1-Chloro-2-methylpropane

CH3 – CH – CH3 2-Chloro-2-methylpropane

1.4 BONDING IN ALKYL HALIDE :

Table : 1 Carbon halogen bond lengths

Bond Bond length(Å)

(d) CH 3 – CH – CH2Cl (e) Isopentyl bromide (f) Neopentyl iodide

Sol. (a) Primary (b) Secondary (c) Tertiary (d) Primary

1.5 PHYSICAL PROPERTIES OF ALKYL HALIDE :

1.5.1 Dipole moment of the halogen derivatives:

Table : 2 Molecular dipole moments of methylhalides

X CH3X CH2X2 CHX3 CX4

Cl 1.94 D 1.60 D 1.03 D 0

Br 1.79 D 1.45 D 1.02 D 0

I 1.64 D 1.11 D 1.00 D 0

1.5.2 Boiling point :

Formula X=F X = Cl X = Br X=I

CH 3– CH2– CH2X –3 47 71 103

CH 3– (CH2)3– CH2X 65 108 129 157

CH 3– (CH2)4– CH2X 92 134 155 180

CH3– CH2F CH3– CHF2 CH3– CF 3 CF3– CF3

1.6 PREPARATION OF ALKYL HALIDE :

1.6.1 From alkane :

1.6.2 From alkenes and alkynes (Detail in alkene and alkyne)

1.6.3 From alcohol (Detail in the alcohol)

1.6.4 From other halides

1.7 CHEMICAL REACTIONS OF ALKYL HALIDE:

1.6.4 Nucleophilic substitution reaction:

(A) Bimolecular nucleophilic substitution reaction (SN2)

(1) It is bimolecular, unistep process

(3) Kinetics of the reaction  rate  [alkyl halide] [nucleophile]

(4) Energetics of the reaction 

(i) Effect of the structure of the substrate 

Table : 6 Relative rates of reactions of alkyl halide in SN2 reaction.

Substituent Compound Relative rate

Neopentyl (CH3)3CCH2X 0.00001

Strong nucleophiles (CH 3CH2)3P Moderate nucleophile : Br

(CH3– CH2) 2NH Cl

(CH3– CH 2)3N Weak nucleophile F

Steric effects on nucleophilicity

In DMSO, the relative order of reactivity of halide ions is

Strongly basic ions rarely act as leaving group 

Br + R – OH R – X + OH (strong base and bad lg)

Nu + CH3 – CH3 CH3 – Nu + CH3 (CH3 is strong base)

Table : 8 Examples of SN2 reactions of alkyl halide 

Nucleophile Product Class of Product

R – X + R' – COO – R – COO – R Ester

(e) + Ph3 P  Salt

Ex. In the given reaction,

Ex. Correct decreasing order of reactivity towards SN2 reaction

What is the function of 8 corwn-6?

(B) Unimolecular nucleophillic substitution reaction (SN1) :